Theoretical study on the potential energy surfaces of hydrated OH and H2O clusters and the singlet-triplet gap of the molecules P(2-py)3M(CO)n(NO)3-n (+3-n), M=Cr, Mo, W; n = 1-3

OH(H2O)nOH(H2O)n+ (n=0-2)

(H2O)n(H2O)n+ (n=1-3)

NgF3- (Ng=Ar, Kr, Xe)

[P(2-py)3M(CO)n(NO)3-n](3-n)+ (M = Cr, Mo, W; n = 13)

OH(H2O)nOH(H2O)n+ (n=0-2)

OHOH () exOH + CH4 H2O+ CH3

OH O3 + h O2+ O O +H2O OH+ OH

OH OH

1977 Hobza Zahradnik OHOH J. Theor. Biol. 1977, 66, 461.

1996Gerakines UVOH(H2O) Astron. Astrophys. 1996,312, 289.

10 K

2000Langford ArOH(H2O) O-H34523428 cm-1 J. Am. Chem. Soc. 2000, 122, 12859.

2003do Couto DFTOH(H2O)n (n=1-6) (H2O)n+1 (n=1-6)OH(H2O) O-H3562 cm-1 J. Chem. Phys. 2003, 119, 7344.

2006 Allodi OH(H2O)n (n=1-5)G3G3B3 OH(H2O)n H2Ofree energy, enthalpy, OH(H2O) J. Phys. Chem. A 2006, 110, 13283.

OHOHOH(H2O)nOH(H2O)nOH(H2O)n+n=0-2OH(H2O)n+OH(H2O)n vertical ionization potentials (VIP)adiabatic ionization potentials(AIP)

MP2, CCSD(T)

aug-cc-pVDZ, aug-cc-pVTZ

Gaussian 03

OHCCSD(T)/aug-cc-pVTZTable 1. OH ()a. Molecular Spectra and Molecular Structure. IV Constants of Diatomic Molecules, Van Nostrand Reinhold Co., 1979

R(O-H) MP2/aug-cc-pVDZ0.975 CCSD(T)/aug-cc-pVTZ0.973 CCSD(T)/aug-cc-pVQZ0.971exp0.970 a

OH... OH2HO...HOHTable 2. OH(H2O) (kcal/mol)(A)(A)a. zero point energy OH(H2O)CCSD(T)/aug-cc-pVTZ

2 H2O (H2O)2 Binding Energies (kcal/mol)Table 3. OH + H2O OH(H2O) Binding Energies ( kcal/mol)a. J. Am. Chem. Soc. 2003, 125, 6048. b. J. Chem. Phys. 2003, 119, 7344.c. J. Phys. Chem. A 2006, 110, 13283.d. J. Phys. Chem. A 2008, 112, 13372.e. J. Chem. Phys. 1979, 71, 2703.f. OH...OH2(H2O)2

EH298KMP2/aug-cc-pVDZ-5.3-3.6CCSD(T)/aug-cc-pVTZ f -5.2-3.6MPW1PW91/aug-cc-pVQZ b-4.6-2.9expe-3.60.48

OH...OH2 E H298KHO...HOHE

MP2/aug-cc-pVDZ-5.9-4.5-3.7CCSD(T)/aug-cc-pVTZ-5.9-4.5-3.7QCISD/6-311++G(2d,2p) a-5.7-3.5MPW1PW91/aug-cc-pVQZ b-5.5-4.1G3 c-4.5CCSD(T)/6-311++G* d-6.1-3.2

NA2 NB2 OH(H2O)2MP2/aug-cc-pVDZTable 4. OH(H2O)2 (kcal/mol)a. b. zero point energy

NA2NB2MP2/aug-cc-pVDZ05.2 (4.1)CCSD(T)/aug-cc-pVTZ a05.3 (4.1)

Table 5. OH + (H2O)2 OH(H2O)2 Binding Energies (kcal/mol)H2O + (H2O)2 (H2O)3 Binding Energies (kcal/mol)a.b. J. Chem. Phys. 2003, 119, 7344.c. J. Phys. Chem. A 2006, 110, 13285.NA2 NA2(H2O)3

NA2E HNB2E

MP2/aug-cc-pVDZ-10.2-8.6-4.9CCSD(T)/aug-cc-pVTZ a-10.3-8.7-5.0MPW1PW91/aug-cc-pVQZ b-8.0G3 c-8.2

EHMP2/aug-cc-pVDZ-11.1 -9.1CCSD(T)/aug-cc-pVTZ a-11.1 -9.1MPW1PW91/aug-cc-pVQZ b-7.9

OH+singlet statetriplet stateCCSD(T)/aug-cc-pVTZTable 6. OH+ (kcal/mol)

STMP2/aug-cc-pVDZ74.90CCSD(T)/aug-cc-pVTZ58.20

OH(H2O)+MP2/aug-cc-pVDZsinglet statetriplet stateSA1SB1TA1TB1TC1Table 7. OH(H2O)+ (kcal/mol)a.

singlettripletSA1SB1TA1TB1TC1MP2/aug-cc-pVDZ83.0 013.9 33.5 43.3CCSD(T)/aug-cc-pVTZ a69.8 016.3 35.0 41.9

OH(H2O)2+MP2/aug-cc-pVDZsinglet statetriplet stateTable 9. OH(H2O)2+ (kcal/mol)SA2SB2TA2TB2TC2SC2a.

singlettripletSA2SB2SC2TA2TB2TC2MP2/aug-cc-pVDZ90.7 013.8 22.0 46.1 49.4CCSD(T)/aug-cc-pVTZ a76.1 012.5 23.2 43.3 48.2

VIP and AIPkcal/molH2O H2O+OH OH+ (singlet or triplet)OHOH+(T)IPOHOH+(S)58 kcal/molOHVIPAIPH2Oa. J. Chem. Phys. 1992, 97, 768b. Proc. R. Soc. London Ser. A 1972, 326, 181.c. zero point energyTable 11. OHsinglet statetriplet stateVIPAIP Table 12. H2Osinglet statetriplet stateVIPAIP

VIPAIPMP2/aug-cc-pVDZ292.8290.8 (289.3)CCSD(T)/aug-cc-pVTZ292.1289.9 (288.3)exp(291.0) b

VIPAIPsinglet triplet singlettriplet MP2/aug-cc-pVDZ370.4295.5369.0294.2 (293.3)cCCSD(T)/aug-cc-pVTZ357.1299.0355.7 297.5 (296.7)cexp(300.2) a

OH(H2O) Table 13. OHsinglet statetriplet stateVIPAIP kcal/molVIPOH...OH2 OH...OH2+ (T)OH...OH2 OH...OH2+ (S)58 kcal/mol AIPOH...OH2 OH(H2O)+ (S) OH...OH2 OH...OH2+ (T) 16 kcal/mola. VIPOH(H2O) OH(H2O)+ (singlet or triplet)AIPOH(H2O) OH(H2O)+ (singlet or triplet)

OH...OH2 to singlet to tripletMP2/aug-cc-pVDZ344.0 270.2CCSD(T)/aug-cc-pVTZ a331.7 273.7

OH...OH2 to SB1to TA1MP2/aug-cc-pVDZ224.6238.5CCSD(T)/aug-cc-pVTZ a224.3240.5

kcal/molVIPNA2 OH(H2O)2+ (T)NA2 OH(H2O)2+ (S)58 kcal/mol AIPNA2 SB2NA2 TA2 23 kcal/molOH(H2O)2 a. Table 14. OHsinglet statetriplet stateVIPAIP VIPOH(H2O)2 OH(H2O)2+ (singlet or triplet)AIPOH(H2O)2 OH(H2O)2+ (singlet or triplet)

NA2to singlet to tripletMP2/aug-cc-pVDZ353.3 281.1CCSD(T)/aug-cc-pVTZ a340.7282.9

NA2to SB2 to TA2MP2/aug-cc-pVDZ196.3218.3CCSD(T)/aug-cc-pVTZ a197.5220.7

Table 15. OH(H2O)nVIP (kcal/mol) OH(H2O)n OH(H2O)n+ (singlet)a. OH(H2O)n OH(H2O)n+ (triplet)

012MP2/aug-cc-pVDZ370.4 344.0 353.3 MP2/aug-cc-pVTZ371.2 346.3 355.6 CCSD(T)/aug-cc-pVTZ a357.3331.7340.7

012MP2/aug-cc-pVDZ295.5 270.2 281.1 MP2/aug-cc-pVTZ298.9 275.1 285.7 CCSD(T)/aug-cc-pVTZ a299.2273.7282.9

H2OAIP Table 16. OH(H2O)nAIP (kcal/mol) OH(H2O)n OH(H2O)n+ (singlet)OH(H2O)n OH(H2O)n+ (triplet)a.

012MP2/aug-cc-pVDZ369.0 224.6 196.3 MP2/aug-cc-pVTZ371.2 223.0 194.4 CCSD(T)/aug-cc-pVTZ a355.7224.3197.5

012MP2/aug-cc-pVDZ294.2 238.5 218.3 MP2/aug-cc-pVTZ298.9 242.6 222.1 CCSD(T)/aug-cc-pVTZ a297.5240.5220.7

Table 17. OHH2O(cm-1) a. Molecular Spectra and Molecular Structure. IV. Constants of Diatomic Molecules, Van Nostrand Reinhold Co., 1979b. Shimanouchi, T. , Tables of Molecular Vibrational Frequencies, Consolidated Volume 1, NSRDS NBS-39

MP2/aug-cc-pVDZMP2/aug-cc-pVTZCCSD(T)/aug-cc-pVTZexpOH O-H3769 (16)3793 (20)37193738 a

H2Obending1622(67)1628(72)16451595 bsymmetrical stretch3803(4)3823(6)38113657 basymmetrical stretch3937(67)3948(75)39203756 a

Table 18. OH(H2O)(cm-1) a. J. Am. Chem. Soc. 2000, 122, 12859.

Table 19. OH+H2O+(cm-1)

MP2/aug-cc-pVDZMP2/aug-cc-pVTZCCSD(T)/aug-cc-pVTZOH+ (S) O-H3154 (308)3178 (317)3153

OH+ (T) O-H3165 (275)3199 (286)3117

H2O+bending1463 (163)1472 (169)1475symmetrical stretch3378 (122)3403 (124)3370asymmetrical stretch3457 (463)3464 (485)3426

Table 20. OH(H2O)+(cm-1) SB1TA1

MP2/aug-cc-pVDZMP2/aug-cc-pVTZCCSD(T)/aug-cc-pVTZSB1 O-H3634 (146)3651 (154)3635H2O symm3474 (238)3496 (246)3526H2O asymm3563 (405)3576 (423)3601

TA1 O-H2824 (1737)2822 (1799)2850H2O symm3642 (221)3659 (215)3663H2O asymm3734 (394)3741 (410)3736

OH(H2O)OH...OH2HO...HOH2.2 kcal/molOH(H2O)2NA2NB25.3 kcal/mol

OH(H2O)n+ (n =1, 2) singlet statehemi-bondedtriplet stateproton transferhemi-bondedproton transfer13-23 kcal/mol

OH(H2O)n+ (n =1,2)OHOH+AIP VIPH2OAIPOH(H2O)n+OH(H2O)nAIPVIP

OH(H2O)n+singlet stateO-O

Lab 409

Vertical Ionization Potentials (VIP) and Adiabatic Ionization Potentials(AIP) VIP AIP back

The Hemibonded Three Electron Systemthree-electron sesquibonded systems (exC2H4+)

oneelectron hemibonded systems bond order=1/2 (exH2+)

Table 8 . OH + H2O+ OH(H2O)+ SB1 Binding Energies (kcal/mol)Table 10. OH + (H2O)2+ OH(H2O)2+ SB2 Binding Energies (kcal/mol)a.

EMP2/aug-cc-pVDZ-150.3 CCSD(T)/aug-cc-pVTZ-137.1

EMP2/aug-cc-pVDZ-64.0 CCSD(T)/aug-cc-pVTZ -61.2 a