CoNO

asakamoto.scc@mbox.nc.kyushu-u.ac.jp

n2n3n1EGround

EGroundJ105

(ab initio)

n2

CoNO-NO -NO -NO

CoNO:IR Spectra(Ar Matrix)a) n1 1761.0 cm-1, n3 620.1 cm-1 DFT calc.a) n2 302.9 cm-1Co CoNO=139b) X3ANLinear moleculea) X1S+CoNOa) : M.Zhou and L. Andrews (2000) b) : C.Blanchet et. al. (1996)O

Electron Configuration of the CoNOCo-NONOCo1Spbdnbsnbsbsabpabp*5s4s3d b : bondingab : anti-bondingnb : non-bonding4F9/22P

PhotolysisUV (193nm)CoNOCoCOCoNOCoCONOCOOCJet cell (56-112 GHz)

Observedspectrum J = 651211, 31303534

Observed spectrum (J = 87)F = J + IJ=8J=7FF59Co I =7/2 11.510.56.59.55.57.58.59.57.58.510.54.55.5CoNO 1SDF=+1DF=0

Molecular constants(1)Constants Unit3s = 26.3 kHzB4669.7514(26)MHz D1.1081(13)kHzeQq168.46(22)MHzCI120.3(48)kHzCoNO ground state:B4 427.009 30(54)MHzD1.130 93(25)kHzeQq-132.0(14)MHz(ref.) CoCO ground state:M. Hayashi (2004)Constants UnitCo

Discussion1.158 (fixed)1.690 FCo-N = 514.7 N/mCoNO1.182 (fixed)1.588 FCo-C = 414.5 N/m(ref.) CoCOM. Hayashi (2004)0.120%

Discussion CILow energy 1P ?(ref.) CI OCS : 2d) kHz ClCN : 3d) HCN : 10d) LiF : 37.3d) DI : 140d) CoC : 447e)d) White,R.L., e) M.Brewster and L. Ziurys (2001)120.3 kHz

0500cm-1n2(P)n3(S)2n2(S)2n2(D)CoNOn1(N-O str.) : 1721.0 cm-1n2 (bending) : 302.9 cm-1n3 (Co-N str.) : 620.1 cm-1Fermi interactionGround

Free space cell (271-326 GHz)CoNOPhotolysisUV (193nm)CoNOCoCONOCOOCCoCO

Observed spectrum (n2)

Observed spectrum (n3)

Observed Spectrum:280318 GHz (J = 30293433)GroundCoNO

Molecular constants(2) Constants n2 state n3 state UnitB4682.8077(22)MHzq5.5918(45)MHza -13.0553(39)MHz4658.455 7(53)0.961 9(25)11.296 7(62)D1.141 5(11)kHzs = 44.4 kHzs = 21.9 kHzqJ0.0114(22)kHz

Molecular constans(2)Constants UnitB24682.8077(22)MHzq5.5918(45)MHza2-13.496(65)MHzn2 stateConstants UnitB34658.4645(53)MHzD30.9631(25)kHzn3 statea311.2869(79)MHzD21.1415(11)kHz3s = 44.4 kHz3s = 21.8 kHzqJ11.4(22)Hz

Vibrationally excited stateCoNOn1(N-O str.) : 1721.0 cm-1n2 (bending) : 302.9 cm-1n3 (Co-N str.) : 620.1 cm-10500

Discussionl-type doubling constant qlVibrational temperaturen2 : 352 Kn3 : 338 Kave. 345 Kcm-1(calc. 302.9 cm-1)

DiscussionFermi interactionn/2(J+1)Groundn2n2n32n2(S)2n2(D)+8.31 MHz-8.31 MHz0500

DiscussionFermi interaction2n2 SDn3 SW223(W223/D)2 = 0.182W223 : D : Y2n2Yn3 18%

DiscussionFermi interaction2n2 SDn3 SD = 0.95 cm-1W223 = 0.40 cm-1n2 = 311 cm-1W223300 cm-1 q2M.Zhou and L.Andrews(2000)

ConclusionCoNOn2n3,2n2-NOCoNO1S

345Kn2w2 = 300 cm-1n32n2Fermi18%kCo-N = 514.7 N/m

Observed spectrum (2n2)

(2)CoNO2DBn3(Co-N str.)w = 638.4 cm-1IR Spectra (Ar matrix) n3 w = 620.1 cm-1D

eQq CoNOCoCOeQq = 168.45 MHzeQq = -131.2 MHzeQq

(2)CISPkkHz CoNO : 120.2 kHzP(1S+)

CoNOcm-1ab initioCoNONOCO2NOx-NO-NONO-NO-NOCoNO2000v1,Co-N1761.0n3N-O620.1n2302.91S3A-NOCoNOCoNOSSNOPNOP*CoCoNOCoCo-NOSCoNOCo(CO)3NOCoNOCoCOCo(CO)3NOCoNO56-112 GHz2BJ=78F=1F=0F=1JJ=5667F=0J561112J=3031343556J7874.6G74.7GHzCoNOCo CoNO1JeQqCoCoNO168MHzNCCoCO-132MHzCoNON-O1.182Co-N1.588CoCOCo-C1.690.1Co-CCoNOFCoN=514.7N/mCoCOFCoC=414.5N/mCo-N20%

n2,n3,2n2introFermiCoNOCo(CO)3NOCoNOCoNOCoNOv2J=32332J350MHzv3v2J=32332(J+1)10MHz1/3v2210MHz1/14v3n22n2CoNOFermiJv24682MHz1.14kHzlql5.6MHzv22-13.5MHzv34660MHz0.9kHzv3311MHzCoNOv1v31721.0620.1v2302.9v2v32v2v32v2v2352Kv3338K345Kn2n2n2300Fermiv3n3n32n2W0.1822n2n318%2v2v3w223CoNOv3620.12v21.30.95w2230.40v2311q2v23002v2J33v227MHz600MHz3Co-N2638.4=620.1