Ultrafast Phenomena V Proceedings of the Fifth O S A Topical Meeting Snowmass, Colorado, June 16-19,1986

Editors: G.R. Fleming and A.E . Siegman

With 427 Figures

Springer-Verlag Berlin Heidelberg New York London Paris Tokyo

Contents

P a r t I M o d e L o c k i n g and U l t r a s h o r t Pulse Generat ion

Passive and H y b r i d Femtosecond O p e r a t i o n o f a L inear A s t i g m a t i s m Compensated Dye Laser B y J . - C . Die ls , N . Jamasb i , and L . Sarger ( W i t h 1 F igure ) 2

G e n e r a t i o n of 55-fs Pulses and Var iab le Spectra l W i n d o w i n g i n a L i n e a r - C a v i t y Synchronously P u m p e d cw Dye Laser B y M . D . D a w s o n , T . F . Boggess, D . W . Garvey, and A . L . S m i r l ( W i t h 4 Figures ) 5

C a v i t y - M i r r o r Dispers ion Dependence of Pulse D u r a t i o n Generated f r o m a Simple C P M Laser: A n E x p e r i m e n t a l Study B y M . Y a m a s h i t a , K . Tor i zuka , T . Sato, and M . Ishikawa ( W i t h 2 Figures) 8

Femtosecond Pulse Generat ion f r o m Passively M o d e Locked Cont inuous Wave Dye Lasers 550-700 n m B y P M . W . French and J .R . Tay lo r ( W i t h 3 Figures) 11

S t a b i l i s a t i o n o f a C P M Dye Laser Synchronously P u m p e d by a Frequency D o u b l e d M L Y A G Laser B y J . Chesnoy and L . F i n i ( W i t h 3 Figures) 14

F l u c t u a t i o n s and C h i r p in Co l l id ing -Pulse Mode-Locked D y e Lasers. B y D . Kühlke, Τ . Bonkho fer , U . Herpers , a n d D . von der L i n d e ( W i t h 2 Figures) 17

E x p e r i m e n t a l Observat ion o f H i g h O r d e r Solitons in a C o l l i d i n g Pulse Mode-Locked Laser B y F . Sa l in , P. Grang ier , G. Roger, and A . B r u n ( W i t h 4 Figures) 20

Advances in the T h e o r y of M o d e - L o c k i n g by Synchronous P u m p i n g . B y G . H . C . New and J . M . C a t h e r a l l ( W i t h 3 Figures) . . . 24

Col lect ive Modes - A n A n a l y t i c a l M o d e l for A c t i v e M o d e L o c k i n g i n the Transient Case B y P. Aechtner , P. He inz , and A . Laubereau ( W i t h 2 Figures) 27

VII

G e n e r a t i o n of Picosecond Pulses f r o m a Cont inuous Wave N e o d y m i u m : P h o s p h a t e Glass Laser B y L . Y a n , J . D . L i n g , P . -T . H o , a n d C . H . Lee ( W i t h 3 F igures ) . . . . 30

P a r t I I U l tra fast O p t i c a l G e n e r a t i o n and M e a s u r e m e n t Techniques

F o u r i e r T r a n s f o r m Picosecond Pulse Shaping and Spec t ra l Phase Measurement i n a G r a t i n g Pulse-Compressor . B y J .P. H e r i t a g e , A . M . Weiner , and R . N . T h u r s t o n ( W i t h 4 F igures ) 34

Picosecond Pulse A m p l i f i c a t i o n U s i n g Pulse Compress ion Techniques. B y D . S t r i c k l a n d , P. M a i n e , M . B o u v i e r , S. W i l l i a m s o n , and G. M o u r o u ( W i t h 4 Figures) 38

New O p t i c a l Design for a Jet A m p l i f i e r . B y O. S e d d i k i , A . G o d d i , R. M o u n e t , J . - F . M o r h a n g e , and C. H i r l i m a n n ( W i t h 2 F igures ) . . . 43

F i b e r R a m a n A m p l i f i c a t i o n So l i ton Laser ( F R A S L )

B y M . N . I s l a m , L . F . Mo l l enauer , a n d R . H . Stolen ( W i t h 4 Figures ) 46

Dispers ion Compensated F i b e r R a m a n Osc i l la tor B y J . D . K a f k a , D . F . H e a d , and T . Baer ( W i t h 2 F igures ) 51 80-fs So l i ton - l ike Pulses f r o m an O p t i c a l N o n l i n e a r F i b e r Resonator . B y B . Zysset, P. B e a u d , W . Hödel , a n d H . P Weber ( W i t h 4 Figures) 54

T h e Stabi l i zed So l i ton Laser B y F . M . Mi t s chke and L . F . M o l l e n a u e r ( W i t h 4 F igures ) 58

T h e So l i ton Self Frequency Shi f t . B y F . M . M i t s c h k e , L . F . M o l l e n a u e r , and J . P G o r d o n ( W i t h 2 F igures ) 62

Sol i tons at t h e Zero Dispers ion Wavelength o f S ing le -Mode Fibers B y P . K . A . W a i , C R . M e n y u k , H . H . C h e n , and Y . C . Lee ( W i t h 1 F i g u r e ) 65

A c t i v e M o d e - L o c k i n g of an I n G a A s P O p t i c a l - F i b e r R i n g Laser B y G . Eisenste in , R . M . Jopson, M . S . W h a l e n , K . L . H a l l , a n d G. R a y b o n ( W i t h 4 Figures ) 68

Femtosecond Resolved Fluorescence B y W . R u d o l p h a n d J . - C . Diels ( W i t h 2 F igures ) 71

P a r a m e t r i c A m p l i f i c a t i o n S a m p l i n g Spectroscopy (PASS) : A New Technique for Reso lv ing N e a r - I n f r a r e d Luminescence on a Subpicosecond T i m e Scale. B y D . H u l i n , A . M i g u s , A . A n t o n e t t i , I . L e d o u x , J . B a d a n , a n d J . Zyss ( W i t h 3 F igures ) 75

VIII

Measurement o f Opt i ca ] Phase w i t h Subpicosecond Reso lut ion by T i m e D o m a i n In ter f e rometry . B y J . E . R o t h e n b e r g ( W i t h 6 F igures ) 78

Rea l T i m e Picosecond O p t i c a l Oscilloscope B y J . A . V a l d m a n i s ( W i t h 8 Figures) 82

B e a m O v e r l a p for L o n g Delay Lines Us ing A c t i v e Feedback B y C. D o l a n d , W . B . Jackson, and A . Andersson ( W i t h 3 Figures) . 86

U l t r a s h o r t Dye Laser Pulses U s i n g the Sweeping O s c i l l a t o r M e t h o d . B y Y . H . Meyer , M . M . M a r t i n , E . B r e h e r e t , a n d 0 . Benois t d ' A z y ( W i t h 4 Figures) 89

A n I n v e s t i g a t i o n on U l t r a s h o r t L i g h t Pulse G e n e r a t i o n by Trave l l ing -Wave A m p l i f i e d Spontaneous E m i s s i o n B y W . Lee, C. N i n g , Z. H u a n g , a n d W . W a n g ( W i t h 5 Figures) . . . 92

P a r t I I I E lectroopt ic S a m p l i n g Techniques

E l e c t r o o p t i c S a m p l i n g o f G a l l i u m Arsen ide I n t e g r a t e d C i r c u i t s B y K . J . W e i n g a r t e n , M . J . W . R o d w e l l , J . L . F r e e m a n , S.K. D i a m o n d , and D . M . B l o o m ( W i t h 6 F igures ) 98

Picosecond C h a r a c t e r i z a t i o n of U l t r a f a s t Phenomena : New Devices and New Techniques. B y D .R . D y k a a r , R. Sobolewski , J . F . W h i t a k e r , T . Y . Hs iang , G .A . M o u r o u , M . A . H o l l i s , B . J . C l i f t o n , K . B . Nichols , C O . Bozler , and R . A . M u r p h y ( W i t h 4 Figures) 103

Precise Measurement of Signal P r o p a g a t i o n Character is t i cs i n G a A s I n t e g r a t e d C i r c u i t s by Picosecond E l e c t r o - O p t i c Sampl ing B y R . K . J a i n , X . - C . Zhang , M . G . Ressl, and T . J . P ier ( W i t h 2 Figures) 107

P r o p a g a t i o n o f U l t r a s h o r t E lec t r i ca l Pulses on Superconduct ing Transmiss ion Lines B y L N . D u l i n g I I I , C . - C C h i , W . J . Gal lagher , D . Grischkowsky, N . J . Halas , M . B . K e t c h e n , and A . W . Kleinsasser ( W i t h 4 Figures) 110

H i g h R e p e t i t i o n Rate E l e c t r o - O p t i c S a m p l i n g w i t h an I n j e c t i o n Laser. B y A . J . Tay lor , R.S. Tucker , J . M . Wiesenfe ld , G. Eisenste in , and C A . B u r r u s ( W i t h 5 Figures) 114

Picosecond Optoe lec tronic Sampl ing of E l e c t r i c a l Waveforms Produced by an O p t i c a l l y E x c i t e d F i e l d Effect Trans i s tor B y D . E . Cooper and S . C Moss ( W i t h 1 F i g u r e ) 117

IX

Picosecond E l e c t r i c a l Pulses i n Microe lec t ron i cs . B y P G . M a y , G . P L i , J . - M . H a l b o u t , M . B . K e t c h e n , C.-C. C h i , M . Scheuermann, I . N . D u l i n g I I I , D . Grischkowsky, a n d M . S m y t h ( W i t h 3 F igures ) . 120

H i g h Speed C i r c u i t Measurements Us ing Photoemiss ion S a m p l i n g B y J . B o k o r , A . M . Johnson , R . H . Storz , and W . M . S impson ( W i t h 2 Figures ) 123

Photoemiss ive S a m p l i n g o f Picosecond E l e c t r i c a l Waveforms B y A . M . Weiner , R . B . M a r c u s , P.S.D. L i n , a n d J . H . Abeles ( W i t h 5 Figures ) 127

Non l inear Responses o f Picosecond Photode tec tors t o Photogenerated Carr i e r s B y T . F . C a r r u t h e r s a n d J . F . Weiler ( W i t h 3 F igures ) 131

D i r e c t Generat i on o f Picosecond t o Subpicosecond O p t i c a l Pulses U s i n g E l e c t r o o p t i c M o d u l a t i o n M e t h o d s B y T . Kobayash i , A . M o r i m o t o , T . F u j i t a , K . A m a n o , T . U e m u r a , a n d T . Sueta ( W i t h 6 Figures) 134

E l i m i n a t i o n o f D y n a m i c F lash i n a Picosecond Streak Image T u b e B y H u a n w e n Zhang ( W i t h 1 F igure ) 137

P a r t I V Nonl inear Optics and C o n t i n u u m G e n e r a t i o n

P a r a m e t r i c C h i r p Reversal and Enhancement : A p p l i c a t i o n i n Femtosecond Opt i cs . B y A . Piskarskas, D . Podenas, A . Stabinis , A . Umbrasas , A . Varanavichius , A . Yankauskas, and G. Yonushauskas ( W i t h 7 Figures) 142

S u p e r c o n t i n u u m Generat ion i n Gases: A H i g h O r d e r Nonl inear Opt i cs Phenomenon . B y P B . C o r k u m , C. R o l l a n d , and T . Sr inivasan-Rao ( W i t h 3 Figures) 149

New E x c i t a t i o n and Probe C o n t i n u u m Sources for Subpicosecond A b s o r p t i o n Spectroscopy B y J . H . G l o w n i a , J . Misewi ch , and P.P. Sorok in ( W i t h 2 Figures) . 153

I n d u c e d Phase M o d u l a t i o n and Spectral B r o a d e n i n g o f a Weak 530-nm Picosecond Pulse by an Intense 1060-nm Picosecond Pulse i n Glass. B y R .R . A l f a n o , Q .X . L i , T . J i m b o , J . T . Manassah , and P.P. H o ( W i t h 2 Figures) 157

T h e Observat ion of C h i r p e d S t i m u l a t e d R a m a n Scat tered L i g h t i n F ibers . B y A . M . Johnson, R . H . Sto len, a n d W . M . S impson ( W i t h 3 Figures ) 160

X

O b s e r v a t i o n o f 7 .2-THz Beats Between the D-L ines o f A t o m i c R b B y J . E . G o l u b and T . W . Mossberg ( W i t h 1 F i g u r e ) 164

Coherent M u l t i p h o t o n Resonant I n t e r a c t i o n a n d H a r m o n i c G e n e r a t i o n . B y A . Mukher j ee , N . M u k h e r j e e , J . - C . Die ls , a n d G. A r z u m a n y a n ( W i t h 4 Figures) 166

U l t r a f a s t Chaos f r o m Semiconductor Lasers. B y Y . C h o , T . U m e d a , I . J u n Cha , M . K o i s h i , and M . M i w a ( W i t h 5 Figures) . 169

P a r t V Applications to Semiconductors , Q u a n t u m Wells , and Solid State P h y s i c s

T h e r m o d y n a m i c s and Kinet ics o f M e l t i n g , E v a p o r a t i o n and C r y s t a l l i z a t i o n , Induced by Picosecond Pulsed Laser I r r a d i a t i o n B y F . Spaepen ( W i t h 1 F igure ) 174

I n v e s t i g a t i o n o f N o n t h e r m a l P o p u l a t i o n D i s t r i b u t i o n s w i t h 10-fs O p t i c a l Pulses. B y C .V . Shank, R . L . Fork , C . H . B r i t o C r u z , a n d W . K n o x ( W i t h 3 Figures) 179

Superheat ing D u r i n g U l t r a f a s t Laser H e a t i n g o f Semiconductors B y D . v o n der L i n d e , Ν. Fabr ic ius , Β. D a n i e l z i k , a n d P. Hermes ( W i t h 4 Figures) 182

N o n - e q u i l i b r i u m Carr iers in G a A s : Secondary E m i s s i o n D u r i n g t h e F i r s t T w o Picoseconds By J . A . K a s h a n d J . C . Tsang ( W i t h 5 F igures ) 188

U l t r a f a s t C a r r i e r Dynamics i n G a A s and A l x G a 1 _ x A s B y W . Z . L i n , J . G . F u j i m o t o , E.P. I p p e n . and R . A . Logan ( W i t h 4 Figures) 193

Subpicosecond O p t i c a l Non- l inear i t i es i n G a A s M u l t i p l e - Q u a n t u m -Wel l S t r u c t u r e s . B y D . H u l i n , A . A n t o n e t t i , A . M i g u s , A . M y s y r o w i c z , H . M . Gibbs , N . P e y g h a m b a r i a n , W . T . Masse l ink , and H . M o r k o g ( W i t h 5 Figures) 197

Picosecond R e l a x a t i o n of N o n t h e r m a l W a n n i e r E x c i t o n s i n GaAs B y L . Schultheis , J . K u h l , A . H o n o l d , and C . W . T u ( W i t h 1 F igure ) 201

Picosecond Observat ion of the Pho tore f rac t i ve Effect i n GaAs B y A . L . S m i r l , G .C . Valley, M . B . K l e i n , K . B o h n e r t , and T . F . Boggess ( W i t h 2 Figures) 203

XI

Time-Reso lved Photo luminescence Measurements i n A l x G a 1 _ x A s U n d e r Intense Picosecond E x c i t a t i o n B y K . B o h n e r t , Η. K a l t , D . P N o r w o o d , Τ .F . Boggess, A . L . S m i r l , a n d R . Y . L o o ( W i t h 2 Figures) 207

Picosecond E x c i t e - P r o b e and Trans ient G r a t i n g Studies o f G a x I n 1 _ x A s y P 1 _ y . B y R . J . M a n n i n g , A . M i l l e r , A . M . Fox, a n d J . H . M a r s h ( W i t h 2 Figures) 210

U l t r a f a s t D y n a m i c s i n G a A l A s D i o d e Laser A m p l i f i e r s B y M . S . S t i x , M . P Kesler , and E.P. I p p e n ( W i t h 8 F igures ) 213

E l e c t r o n i c Energy R e l a x a t i o n and L o c a l i z a t i o n i n T w o I I - V I C o m p o u n d Semiconductor Q u a n t u m Wel l Structures B y Y . Hefetz , W . C . Goltsos, D . Lee, and A . V . N u r m i k k o ( W i t h 6 Figures ) 218

T r a n s i e n t R a m a n Scat ter ing i n M u l t i p l e Q u a n t u m W e l l S tructures B y D . Y . O b e r l i , D . R . Wake, M . V . K l e i n , J . K l e m , a n d H . M o r k o g ( W i t h 2 Figures) 223

Fast E n e r g y R e l a x a t i o n of H o t Electrons i n B u l k G a A s a n d M u l t i -Q u a n t u m Wells . B y C . H . Yang and S.A. L y o n ( W i t h 2 Figures) . . . 227

Picosecond Photo luminescence and Energy-Loss Rates i n G a A s Q u a n t u m Wells U n d e r H i g h - D e n s i t y E x c i t a t i o n B y T . Kobayash i , H . U c h i k i , Y . A r a k a w a , and H . Sakaki ( W i t h 4 Figures) 231

B r o a d T u n i n g o f the Photo luminescence Energy and L i f e t i m e by t h e Q u a n t u m - C o n f i n e d Stark Effect . B y H . - J . P o l l a n d , L . Schultheis , J . Kühl , E .O . Göbel , and C . W . T u ( W i t h 2 Figures ) 234

A u g e r H e a t i n g of Si l i con-on-Sapphire by Femtosecond O p t i c a l Pulses . B y M . C . D o w n e r and C.V. Shank ( W i t h 2 F igures ) 238

T h e O r i g i n o f Picosecond P h o t o i n d u c e d A b s o r p t i o n Decays i n H y d r o g e n a t e d A m o r p h o u s Sil icon B y W . B . Jackson, C. D o l a n d , and C.C. T s a i ( W i t h 2 F igures ) 242

Picosecond Decay of P h o t o i n d u c e d A b s o r p t i o n i n H y d r o g e n a t e d A m o r p h o u s Si l i con B y D . M . Rober t s a n d T . L . Gustafson ( W i t h 2 F igures ) 245

Femtosecond Spectroscopy of H o t Carr iers i n G e r m a n i u m B y P . M . Fauchet , D . H u l i n , G . H a m o n i a u x , A . Orszag, J . Kolodzey , a n d S. Wagner ( W i t h 3 Figures) 248

XII

Sp in D ephas i ng Kinet i cs of Free Carr iers i n A l l o y Semimagnet ic Semiconductors C d j _ x M n x S e by One and T w o P h o t o n E x c i t a t i o n B y M . R . J u n n a r k a r and R.R. A l f a n o ( W i t h 1 F igure ) 251

D e t e c t i o n o f Higher Order Fourier Components o f Index G r a t i n g s i n Picosecond Transient G r a t i n g E x p e r i m e n t s B y E . O . Göbe l and H . Saito ( W i t h 3 F igures ) 254

T r a n s i e n t Thermoref lectance Studies of T h e r m a l T r a n s p o r t i n C o m p o s i t i o n a l l y M o d u l a t e d M e t a l F i l m s . B y G . L . Eesley, C . A . Paddock , and B . M . Clemens ( W i t h 2 Figures) 257

Femtosecond Studies of N o n e q u i l i b r i u m Elec t ron i c Processes i n M e t a l s . B y R . W . Schoenlein, W . Z . L i n , J . G . F u j i m o t o , a n d G . L . Eesley ( W i t h 4 Figures) 260

T ime-Reso lved Observat ion of E l e c t r o n - P h o n o n R e l a x a t i o n D u r i n g Femtosecond Laser Heat ing o f Copper . B y H . E l s a y e d - A l i , M . Pessot, T . N o r r i s , and G. M o u r o u ( W i t h 2 F igures ) 264

Femtosecond C a r r i e r Re laxat i on i n Semiconduc tor -Doped Glasses B y M . C Nuss, W . Z i n t h , and W . Kaiser ( W i t h 2 Figures ) 267

Femtosecond Dynamics o f E lec t ron -Ho le P lasma i n Semiconductor M i c r o c r y s t a l l i t e Doped Glass. B y C R . O l b r i g h t , B . D . Fluegel , S .W. K o c h , and N . Peyghambar ian ( W i t h 2 F igures ) 270

H i g h - C o n t r a s t U l t r a f a s t Phase C o n j u g a t i o n i n Semiconductor -D o p e d Glass. B y D . C o t t e r ( W i t h 3 Figures) 274

Femtosecond V i b r a t i o n a l Re laxat i on of the F \ Center i n L i F B y W . H . K n o x , L . F . Mo l l enauer , and R . L . Fork ( W i t h 2 Figures) . 277

D e t e r m i n a t i o n of the R a p i d Quenching Rates of E x c i t e d State F-Centers by O H ~ Defects i n K C l . B y D u - J e o n J a n g , T . C C o r c o r a n , M . A . El -Sayed, L . Gomes, a n d F . L u t y ( W i t h 4 Figures) 280

P r o p a g a t i o n of Coherent Phonon Po lar i tons i n L i T a 0 3 Measured by FIR-Cherenkov-Pulses B y M . C . Nuss and D . H . A u s t o n ( W i t h 3 F igures ) 284

P a r t V I C h e m i c a l React ion D y n a m i c s

Cages, Crossings and Corre lat ions - T h e o r e t i c a l Perspectives on So lut i on React ion D y n a m i c s . B y J . T . Hynes 288

XIII

P o l a r i t y Dependent B a r r i e r s and the P h o t o i s o m e r i z a t i o n D y n a m i c s o f Po lar Molecules i n S o lu t i o n . B y J . M . Hicks , M . T . Vandersa l l , E . V . S i t z m a n n , and K . B . Eisenthal ( W i t h 3 F igures ) 293

D y n a m i c Solvent Effects on Smal l B a r r i e r I somer izat ions B y P .F . B a r b a r a and V . Nagara jan ( W i t h 3 F igures ) 299

Solvat ion D y n a m i c s i n Po lar L i q u i d s : E x p e r i m e n t and S i m u l a t i o n B y M . M a r o n c e l l i , E . W . Castner , J r . , S.P. Webb , a n d G.R. F l e m i n g ( W i t h 4 Figures) 303

Femtosecond S tudy o f E l e c t r o n L o c a l i z a t i o n a n d So lvat ion i n P u r e Water . B y Y . G a u d u e l , J . L . M a r t i n , A . M i g u s , N . Y a m a d a , a n d A . A n t o n e t t i ( W i t h 2 Figures) 308

T i m e - D e p e n d e n t Fluorescence Shi f t i n A lcoho l i c Solvents: A Non-Debye Behav iour Related t o H y d r o g e n Bonds B y C. R u l l i e r e , A . Declemy, and P h . K o t t i s ( W i t h 4 Figures ) 312

Picosecond D y n a m i c s o f P r o t o n - A n i o n I o n P a i r G e m i n a t e R e c o m b i n a t i o n . B y D . H u p p e r t a n d E . Pines ( W i t h 1 F i g u r e ) 315

E x c i t e d State P r o t o n Transfer i n M a t r i x Iso lated W a t e r and M e t h a n o l Complexes o f 2 -Hydroxy -4 ,5 -benzotropone a n d 3 -Hydroxyf lavone B y D . F . Ke l l ey and G . A . Brucker ( W i t h 2 Figures ) 319

Detec t i on o f t h e I n v e r t e d Region i n P h o t o - i n d u c e d I n t r a m o l e c u l a r E l e c t r o n Transfer . B y R . J . H a r r i s o n , G.S. B e d d a r d , J . A . Cowan , and J . K . M . Sanders ( W i t h 2 Figures ) 322

U l t r a f a s t Studies Designed t o Test t h e F u n d a m e n t a l S t a t i s t i c a l Assumpt ions U n d e r l y i n g Chemica l R e a c t i v i t y i n L i q u i d s B y C .B . H a r r i s , J . K . B r o w n , M . E . Paige, D . E . S m i t h , and D . J . Russell ( W i t h 4 Figures) 326

Geminate R e c o m b i n a t i o n and R e l a x a t i o n o f Condensed Phase Molecu lar Halogens B y D . F . Kel ley and N . A . A b u l H a j ( W i t h 1 F i g u r e ) 330

Fast Photochemica l Processes o f A r o m a t i c N i t r o C o m p o u n d s in So lu t i on . B y B . B . C r a i g , S.K. C h a t t o p a d h y a y , and J . C . M i a l o c q ( W i t h 4 Figures) 334

Cage Recombinat i on and U n i m o l e c u l a r /?-Scission React ions o f Sul fur Centered Free Radicals B y T . W . Scott and S.N. L i u ( W i t h 3 F igures ) 338

XIV

T h e I n f l u e n c e of F r i c t i o n and D e u t e r a t i o n on St i lbene I s o m e r i z a t i o n . B y S.H. Courtney , M . W . B a l k , S. Canonica , S.K. K i m , a n d G.R. F l e m i n g ( W i t h 3 Figures) 341

K r a m e r s - H u b b a r d A p p r o a c h t o the Solvent Dependence of I s o m e r i z a t i o n . B y M . Lee and R . M . Hochstrasser ( W i t h 3 Figures) 344

P h o t o i s o m e r i z a t i o n Studies o f S u b s t i t u t e d Sti lbenes: 4,4 ' -D i h y d r o x y s t i l b e n e and 4 ,4 ' -D imethoxy st i lbene B y D . M . Zeg l insk i and D . H . Waldeck ( W i t h 2 Figures) 347

Picosecond Studies of Barrierless Tors iona l Di f fus ion B y D . B e n - A m o t z and C .B . H a r r i s ( W i t h 2 Figures) 350

T i m e - R e s o l v e d Fluorescence Spectra of E t h i d i u m B r o m i d e B y J . H . S o m m e r , Τ . Μ . N o r d l u n d , Μ. M c G u i r e , a n d G. M c L e n d o n ( W i t h 3 F igures ) 353

Picosecond a n d Femtosecond M o l e c u l a r Beam C h e m i s t r y : Coherence a n d Fragment Recoi l D y n a m i c s By A . H . Zewai l ( W i t h 4 Figures) 356

Picosecond Laser Study of the Collisionless U V Photod issoc ia t i on of E n e r g e t i c M a t e r i a l s By J . - C . M i a l o c q and J . C . Stephenson ( W i t h 3 Figures) 362

E x p e r i m e n t a l S tudy of H a r m o n i c Generat i on w i t h Picosecond 248 n m R a d i a t i o n . B y T .S . L u k , A . M c P h e r s o n , H . J a r a , U . J o h a n n , I . A . M c l n t y r e , A . P . Schwarzenbach, Κ. Boyer , and C . K . Rhodes ( W i t h 2 Figures) 366

T ime -Reso lved Measurement of Laser - Induced D e s o r p t i o n of a M o l e c u l a r Monolayer . B y G . A r j a v a l i n g a m , T . F . H e i n z , and J . H . G l o w n i a ( W i t h 1 F igure ) 370

P a r t V I I D y n a m i c s of Biological Processes

Picosecond E l e c t r o n Transfer and S t i m u l a t e d Emiss ion i n Reac t i on Centers o f Rhodobacter sphaeroides and Chlorofelxus aurantiacus. B y M . Becker, D . M i d d e n d o r f , N . W . W o o d b u r y , W . W . P a r s o n , and R . E . B lankensh ip ( W i t h 4 F igures ) 374

Femtosecond Spectroscopy of the P r i m a r y Events o f B a c t e r i a l Photosynthes is B y W . Z i n t h , J . Dobler , and W . Kaiser ( W i t h 3 Figures) 379

A n A c c u m u l a t e d P h o t o n Echo Study of Sub-picosecond Processes i n P h o t o s y n t h e t i c React ion Centers B y S.R. Meech, A . J . Hoff , and D . A . W i e r s m a ( W i t h 2 Figures) . . . . 384

XV

U l t r a f a s t E l e c t r o n and Energy Transfer in React ion Center and A n t e n n a Prote ins f r o m Photosynthet i c B a c t e r i a B y M . R . Wasie lewski , D . M . T iede , and H . A . F r a n k ( W i t h 5 Figures) 388

Femtosecond Spectroscopy of E x c i t a t i o n Energy Transfer and I n i t i a l Charge Separat ion i n the React ion Center o f t h e Photosynthet i c B a c t e r i u m Rhodopseudomonas sphaeroides B y J . B r e t o n , J . - L . M a r t i n , A . M i g u s , A . A n t o n e t t i , and A . Orszag ( W i t h 4 Figures) 393

Picosecond Trans ient A b s o r p t i o n Spectroscopy of Green P l a n t Photosystem I React ion Centres B y B . L . Gore , L . B . G i o r g i , and G. Por te r ( W i t h 1 F i g u r e ) 398

Femtosecond-Pulse Spectroscopy of P r i m a r y Photoprocesses i n React ion Centers o f Rhodopseudomonas sphaeroides R-26 B y S.V. C h e k a l i n , Y u . A . Matvee ts , and A . P . Yartsev ( W i t h 3 Figures ) 402

Detergent Effects u p o n the Picosecond D y n a m i c s o f H i g h e r P l a n t L i g h t H a r v e s t i n g C h l o r o p h y l l Complex ( L H C ) . B y J .P. I d e , D . R . K l u g , W . K u h l b r a n d t , G. Por ter , and J . B a r b e r ( W i t h 1 F igure ) 406

Picosecond C o n f o r m a t i o n a l Intermediates i n t h e B a c t e r i o r h o d o p s i n Photocyc le . B y G . H . A t k i n s o n , T . L . Brack , D . B l a n c h a r d , G . Rumbles , a n d L . Siemankowski ( W i t h 3 F igures ) 409

E l e c t r o n Transfer and R a p i d Restr i c ted M o t i o n i n Homologous A z u r i n s . B y J . W . P e t r i c h , J . W . L o n g w o r t h , and G.R. F l e m i n g ( W i t h 3 Figures ) 413

P r i m a r y Process o f V i s i o n : Hypsorhodops in B y T . Kobayash i , H . O h t a n i , and M . T g u d a ( W i t h 3 F igures ) 416

R e a c t i v i t y and Dynamics of Hemeprote ins i n the Femtosecond a n d Picosecond T i m e Domains . B y D . Houde , J . W . P e t r i c h , O . L Ro jas , C. Poyar t , A . A n t o n e t t i , and J . L . M a r t i n ( W i t h 3 F igures ) 419

Picosecond R a m a n Hole B u r n i n g as a Probe of C o n f o r m a t i o n a l Heterogeneity : A p p l i c a t i o n s t o O x y h e m o g l o b i n B y B . F . C a m p b e l l and J . M . F r i e d m a n ( W i t h 4 F igures ) 423

U l t r a f a s t Studies of N i t r o s y l m y o g l o b i n . B y K . A . J o n g e w a r d , J . C . M a r s t e r s , and D . M a g d e ( W i t h 4 Figures ) 427

Molecu lar D y n a m i c s S tudy of V i b r a t i o n a l C o o l i n g i n O p t i c a l l y E x c i t e d Hemeprote ins . B y E.R. H e n r y , W . A . E a t o n , a n d R . M . Hochstrasser ( W i t h 1 F igure ) 430

XVI

C h e m i c a l React ion in a Glassy M a t r i x : D y n a m i c s o f L i g a n d B i n d i n g t o Pro toheme i n G lycero l :Water . B y J . R . H i l l , M . J . Cote , D . D . D l o t t , J . F . K a u f f m a n , J . D . M c D o n a l d , P . J . Ste inbach, J . R . Berendzen , and H . Frauenfelder ( W i t h 3 F igures ) 433

P a r t V I I I E n e r g y Transfer and R e l a x a t i o n

Energy and E l e c t r o n Transfer of Adsorbed Dyes on M o l e c u l a r Single Crysta l s and O t h e r Substrates . B y K . K e m n i t z , Ν. Nakash ima , and K . Yosh ihara ( W i t h 5 F igures ) 438

O p t i c a l P u m p - P r o b e Spectroscopy of Dyes on Surfaces: G r o u n d -State Recovery of R h o d a m i n e 640 on Z n O a n d Fused Si l i ca B y P .A. A n f i n r u d , T . P Causgrove, a n d W.S . S t r u v e ( W i t h 1 F igure ) 442

Picosecond Fluorescence Spectroscopy on M o l e c u l a r Assoc iat ion in L a n g m u i r - B l o d g e t t F i l m s B y I . Y a m a z a k i , N . T a m a i , and T . Y a m a z a k i ( W i t h 3 Figures ) 444

Fluorescence Concentra t i on D e p o l a r i z a t i o n o f D O D C I i n G lycero l : A P h o t o n - C o u n t i n g Test of T h r e e - D i m e n s i o n a l E x c i t a t i o n T r a n s p o r t T h e o r y B y D . E . H a r t , P.A. A n f i n r u d , and W.S . S t ruve ( W i t h 1 F igure ) . . . 447

F r a c t a l Behaviors i n T w o - D i m e n s i o n a l E x c i t a t i o n E n e r g y Transfer o n Vesicle Surfaces. B y N . T a m a i , T . Y a m a z a k i , I . Y a m a z a k i , a n d N . M a t a g a ( W i t h 3 Figures) 449

Trans ient V i b r a t i o n a l H e a t i n g of Molecules A f t e r I n t e r n a l Convers ion. B y A . Seilmeier, U . Sukowski , W . Kaiser , a n d S.F. Fischer ( W i t h 2 Figures) 454

Non l inear A b s o r p t i o n Spectroscopy of L i q u i d s w i t h U l t r a s h o r t I R Pulses B y H . Graener , R. Dohlus , and A . Laubereau ( W i t h 2 Figures) — 458

Femtosecond Re laxat ion Dynamics of Large Organic Molecules B y M . J . Rosker, F . W . Wise , C .L . Tang , and A . J . T a y l o r ( W i t h 4 Figures) 461

P o p u l a t i o n L i f e t imes of O H ( v = l ) and O D ( v = l ) V i b r a t i o n s i n Alcohols , Silanols and C r y s t a l l i n e Micas . B y E . J . H e i l w e i l , Μ.P. Casassa, R .R . Cavanagh, and J . C . Stephenson 465

S 0 - S n T w o - P h o t o n A b s o r p t i o n D y n a m i c s o f R h o d a m i n e Dyes B y P. Sperber, Μ. Weidner , and A . Penzkofer ( W i t h 3 Figures) — 469

XVII

Nonl inear O p t i c a l Response of One -Dimens iona l E x c i t o n s i n Po lydiacety lene . B y B . I . Greene, J . Orens te in , R .R . M i l l a r d , and L . R . W i l l i a m s ( W i t h 2 Figures) 472

Picosecond P h o t o c o n d u c t i v i t y and Non l inear O p t i c a l Phenomena i n i rans -Po lyace ty lene B y D . Moses, M . S inc la ir , and A . J . Heeger ( W i t h 1 F i g u r e ) 475

Singlet E x c i t o n Fusion i n Mo lecu lar Solids B y R .R . M i l l a r d a n d B . I . Greene ( W i t h 2 Figures ) 478

M a t r i x Effect o n V i b r a t i o n a l R e l a x a t i o n i n M o l e c u l a r Crys ta l s B y J .R . H i l l , E . L . C h r o n i s t e r , J . C . Post lewaite , and D . D . D l o t t ( W i t h 1 F i g u r e ) 482

O p t i c a l Damage i n M o l e c u l a r Crysta l s : A Sol id State Exp los i on B y D . D . D l o t t , T . J . Kos ic , and J .R . H i l l ( W i t h 4 F igures ) 485

R o t a t i o n a l R e l a x a t i o n o f Free a n d Solvated Rotors B y A . J . B a i n , C. H a n , P . L . H o l t , P .J . M c C a r t h y , A . B . M y e r s , M . A . Pere ira , a n d R . M . Hochstrasser ( W i t h 5 Figures ) 489

U l t r a f a s t D y n a m i c s at t h e Inter face : P r o b i n g t h e T r a n s i t i o n f r o m So lu t i on t o Surface In terac t i ons i n Charged Micel les B y E . F . T e m p l e t o n , K . B r i n k e r , S. Paone, a n d G . A . K e n n e y -Wallace ( W i t h 1 F i g u r e ) 495

Shock M o d e r a t e d Photophysics and Photo chemis t ry at M u l t i -k i l o b a r Pressures B y B . L . Justus , A . L . H u s t o n , and A . J . C a m p i l l o ( W i t h 5 Figures ) . 499

P a r t I X Coherent Spectroscopic Techniques

Phase G r a t i n g A p p r o a c h t o Suscept ib i l i ty Tensors: D e t e r m i n a t i o n i n I so t rop i c M e d i a . B y J . Etchepare , G. G r i l l o n , I . T h o m a z e a u , G. H a m o n i a u x , and A . Orszag ( W i t h 4 Figures) 504

Non l inear Response F u n c t i o n for Four-Wave M i x i n g : A p p l i c a t i o n t o Coherent R a m a n Lineshapes i n Po lyatomics and t o t h e O p t i c a l A n d e r s o n T r a n s i t i o n B y S. M u k a m e l , Z. Deng , and R . F . L o r i n g ( W i t h 2 Figures) 510

Picosecond Laser Pulse Shaping and Phase S h i f t i n g for M o l e c u l a r Spectroscopy B y M . Haner , F . Spano, and W.S . W a r r e n ( W i t h 2 Figures) 514

T h i r d - O r d e r Non l inear O p t i c a l Interac t i ons i n T h i n F i l m s o f Organic Po lymers Invest igated by Picosecond and Subpicosecond Four-Wave M i x i n g . B y P . N . Prasad , D . Narayana Rao, J . Swiatk iewicz , P. C h o p r a , and S.K. Ghoshal 518

XVIII

Picosecond Raman- Induced Phase C o n j u g a t i o n Spectroscopy B y R. D o r s i n v i l l e , P. De l fyet t , a n d R.R. A l f a n o ( W i t h 2 Figures) . . 521

P o l a r i z a t i o n Dependence of T ime-Reso lved C A R S i n L i q u i d s B y N . Kohles and A . Laubereau ( W i t h 3 F igures ) 524

D i r e c t Measurement of Wave-Vector -Dependent P o l a r i t o n Energy Ve loc i ty a n d Dephas ing i n N H 4 C 1 B y G . M . Gale , F . Vallee, and C. F ly t zan i s ( W i t h 4 Figures) 528

I m p u l s i v e S t i m u l a t e d Rayle igh , B r i l l o u i n , a n d R a m a n Scat ter ing : E x p e r i m e n t s and T h e o r y of L i g h t Scat ter ing Spectroscopy i n the T i m e D o m a i n . B y M . R . Farrar , L . R . W i l l i a m s , Y o n g - X i n Y a n , L a p - T a k C h e n g , and K . A . Nelson ( W i t h 4 F igures ) 532

U l t r a f a s t Trans ient Spectroscopy w i t h B r o a d b a n d N o n - T r a n s f o r m -L i m i t e d L i g h t Sources B y T . Y a j i m a a n d N . M o r i t a ( W i t h 4 Figures) 536

Picosecond Dephasing T i m e Measurement by CSRS U s i n g T e m p o r a l l y Incoherent Nanosecond Laser w i t h Short C o r r e l a t i o n T i m e B y T . K obayas h i , T . H a t t o r i , and A . Terasaki ( W i t h 3 Figures) . . . 541

A n o m a l o u s Pulse D u r a t i o n Dependence of the Q u a s i c o n t i n u u m A b s o r p t i o n S p e c t r u m B y P. M u k h e r j e e and H.S. K w o k ( W i t h 3 Figures) 544

I n d e x of C o n t r i b u t o r s 549

XIX

Femtosecond Spectroscopy of the P r i m a r y Events of Bacter ia l Photosynthesis

W. Zinth, J. Dobler, and W. Kaiser

Phys ik D e p a r t m e n t der Technischen Universität München, Arcisstraße 2 1 , D-8000 München 2, Fed. Rep. of Germany

Recent investigations of bacterial photosynthesis have shown that the primary steps occur on the time scale of one picosecond /1-3/. These processes can only be studied by means of ultrafest optical techniques. The standard experimental methods yield absorption changes induced by a short excitation pulse measured as a function of time and wavelength. Experiments are now possible with the temporal resolution of better than 100 f s . They present interesting information on the early dynamics of the primary processes. Optical techniques alone provide insufficient understanding of the molecular microscopic processes of the primary steps. I t i s important to add information from other experiments, e.g. from structure analysis, resonance Raman scattering, molecular dynamics calculations or experiments on model compounds.

In this note we are concerned with time-resolved experiments of the primary steps of photosynthetic units such as bacteriorhodopsin and bacterial reaction centers. We combine the results of ultrafast spectroscopy with other available data in order to gain a better insight into the molecular processes of the primary events.

Experimental

The experiments are performed using amplified pulses (tP=100 f s ,

repetition rate 7.5 kHz) from a colliding pulse mode-locked laser operating at 620 nm for the excitation of the samples. Probing pulses are obtained by continuum generation in a j e t of ethylene glycol. A narrow fraction of the continuum (Δλ

s

10-15 nm) was selected. The probe pulses monitor the absorbance changes of the sample as a function of time delay between exciting and probing pulses. In order to avoid high exposure the sample was kept in a spinning cuvette. In this way, i t was ascertained that each photosynthetic unit absorbs one photon only every second. There was no indication of any photodecomposition of the samples at the excitation densities used in the experiments (less than 10% of the molecules absorb one photon per excitation pulse).

Bacteriorhodopsin Bacteriorhodopsin (BR) i s a membrane protein contained in the c e l l membrane of Halobacterium halobium. I t acts as a light-driven proton pump building up a proton gradient across the c e l l membrane upon illumination.

The absorption properties of BR are determined by the only pigment molecule r e t i n a l . Retinal i s bound in BR via a Schiff base to one lysine of the polypeptide chain. In the light-adapted form of BR, the retinal molecule has the all-trans configuration and the Schiff base i s protonated. During the photochemical cycle the absorption properties of BR change substantially. Intermediate states named J,K,L,M,... have been

379

Fig,1 Bacteriorhodopsin: Absorption changes induced by 100 fs excitation pulses at 620 run

D e l a y T i m e t D CpsD

identified. During the course of the cycle the retinal adopts the 13-cis configuration and the Schiff base loses i t s proton. The photochemical cycle i s completed after ~ 10 ms. The f i r s t events of the photocycle of BR, where the optical energy i s stored in the molecules, have been studied in a number of publications. I t was not until recently, that a coherent picture of the primary molecular process was presented /1,4,5/.

Fig.1 shows absorption changes measured as a function of time delay after excitation of the BR molecules at 620 nm. When the molecules are probed at 490 nm, a strong induced absorption i s found which builds up with the time resolution of the experiment of 100 f s . In a f i r s t relaxation process this absorption change decays with a time constant of 430 fs into a state of reduced absorption from which a slow 5 ps kinetic leads to a partial recovery of the absorption, which stays constant for times longer than 12 ps (not shown in F i g . l ) . The same time constants (< 100 f s , 430 f s , and 5 ps) are found at the other probing wavelengths of 545 nm and 620 nm in Fig.lb and c, respectively.

The results presented above together with additional information from femtosecond experiments on deuterated BR / l / , from picosecond data on BR containing a s t e r i c a l l y fixed retinal molecule /6/, and from resonance Raman

380

scattering /7/ yield the following microscopic picture of the primary molecular processes: Light promotes BR to a Franck-Condon state on the excited-state potential surface. From there a very fast (τ < 100 fs) molecular motion leads to the bottom of the Si potential surface. Internal conversion with τ' = 430 fs leads to the ground state intermediate J which contains the isomerized 13-cis r e t i n a l . Rearrangements of the protein surrounding causes the slower 5 ps kinetics leading to the intermediate Κ which i s stable for the longer time of 300 ps.

Reaction Centers Photosynthesis in green plants and in most bacterial systems uses chlorophyll or bacteriochlorophyll molecules arranged in so-called reaction centers (RC) where a primary charge separation i s ini t i a t e d . Reaction centers can be isolated from some bacteria. The reaction centers of Rhodopseudomonas v i r i d i s or Rhodopseudomonas spheroides contain six pigments absorbing in the visible and near infrared: 4 bacteriochlorophyll (BCl) and 2 bacteriopheophytin (BPh) of type b and a for R-viridis and R-spheroides, respectively. Two of the BCl form the excitonically coupled special pair, from which the charge separation originates. A major progress in the understanding of the molecular processes in the RC was recently achieved when the reaction centers of R-viridis were crysta l l i z e d /8/ and when a structural analysis of these RC was completed /9/. The arrangement of pigments obtained by structure analysis allowed claculation of the excitonic coupling: i t was shown that there i s strong excitonic mixing between the various pigments of the RC, substantially influencing the absorption in the near infrared spectral region (λ > 750 nm) /10/.

I t i s the purpose of this chapter to compare the dynamic absorption changes in R-viridis - where the pigment arrangement i s known - with those of R-spheroides. In addition, the data give information on excitation transfer between the pigments in the RC. Because of the strong excitonic interaction which influences the IR absorption bands we concentrate here on the v i s i b l e absorption where the Qx transitions are located. BCl absorbs around 600 nm, BPh around 540 nm and - in the RC of R-viridis - the special pair (P) exhibits a shoulder in the absorption around 620 nm.

Time-resolved absorption measurements are shown in Fig.2 for R-viridis (a,b) and R-spheroides (c,d) after excitation at 620 nm. F i r s t we probed around 545 nm at a frequency where the BPh absorbs. The data show at later delay times, i.e. for to > 200 fs a decay of the absorption with a time constant of 2.8 ps for both types of RC. The absorption decreases at 545 nm, where i n i t i a l l y the BPh's absorb strongly suggesting that BPh i s reduced to form BPh". Additional experiments at λ = 675 nm, a wavelength where BPh" absorbs, support this interpretation. Figs. 2b and d show the rise of the absorption change on an expanded scale. In both cases the rise follows closely the integrated cross-correlation curve between exciting and probing pulses. We may deduce from these data that the absorption appears within our time resolution of 100 fs for the RC of R-viridis and R-spheroides. The molecular nature of this early state requires some consideration. I t may simply be the excited electronic state P* of the special pair or i t i s a state P+~ which contains considerable contribution from a charge transfer state /2/. Both interpretations are possible within the scope of present knowledge.

The experimental findings of the two time constants of < 100 fs and 2.8 ps allow us to draw the following conclusions: After absorption of a photon at 620 nm the excitation i s rapidly transferred, τ < 100 f s , to

381

the special pair to form the primary state P* or P+

~. Subsequently, reduction of BPh to BPh" occurs within 2.8 ps. Since both systems, the RC of R-viridis and of R-spheroides, behave in the same manner, we believe that their pigment arrangements and the interactions between the pigments are very similar.

Conclusions

The present investigations of the bacterial photosynthesis of two very different photosynthetic systems - bacteriorhodopsin and bacterial reaction centers -suggest very high reaction rates of the primary events. This common property can be well understood with the help of the reaction scheme shown in Fig.3. After optical excitation^fast molecular rearrangements occur on the excited-state potential surface. From there two pathways are possible: internal conversion to the i n i t i a l ground

R e a c t i o n C o o r d i n a t e :

C h a r g e T r a n s f e r ( R C ) I s o m e r i z a t i o n ( O R )

Fig.3 Schematic of the energy surfaces indicating the primary reactions in the investigated photosynthetic systems

382

state and the desired photochemical reaction. The internal conversion rates for most large pigment systems are very rapid. For this reason, the reactive channel must be faster in order to maintain reasonable quantum efficiencies in the f i r s t photosynthetic steps.

Acknowledgemen t The authors gratefully acknowledge valuable contributions from H.Michel, D.Oesterhelt, and H. Scheer.

1 M.C. Nuss, W. Zinth, W. Kaiser, E. Rolling, D. Oesterhelt, Chem. Phys. Lett. 117 (1985) 1

2 J.-L. Martin, J . Breton, A. J . Hoff, A. Migus, A. Antonetti, Proc. Nat. Acad. Sei. USA 83 (1986) 957

3 W. Zinth, M.C. Nuss, M.A. Franz, W. Kaiser, H. Michel, in "Antennas and Reaction Centers of Photosynthetic Bacteria", ed. M.E. Michel-Beyerle, Springer, Berlin 1985, p.286

4 H.J. Polland, M.A. Franz, W. Zinth, W. Kaiser, E. Rolling, D. Oesterhelt, Biophys. J . 49 (1986) 651; H.J. Polland, W. Zinth, W. Raiser, in "Ultrafast Phenomena IV", ed. D.H. Auston, R.B. Eisenthal, Springer Series in Chem. Phys., Springer, Heidelberg 1984, p. 456

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