Summary
An extension of the multiconfigurational SCF approach for the resolution of the vibrational problem is presented; it follows the philosophy of the CASSCF method developed in Quantum Chemistry. The new method allows a more complete treatment of anharmonic mode couplings, converges much faster and gives a clearer physical insight of vibrational interactions. This is exemplified by the calculation of infrared transition moments in the H2O and D2O isotopomers of the water molecule. It is shown how this property varies with the quality of the wave function when vibrational resonances occur. A detailed analysis by means of this new VCASSCF method demonstrates the crucial importance of excited bending oscillators in the intensity of some pure stretching transitions.
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References
Culot F, Liévin J (1994) Theoret Chim Acta 89:227
Roos BO (1987) In: Lawley KP (ed) Advances in chemical physics,ab initio methods in quantum chemistry, Part 2, Vol LXVII. Wiley, New York, p 399
Ruedenberg K, Schmidt MW, Gilbert MM, Elbert ST (1982) Chem Phys 71:41
Grein F, Chang TC (1971) Chem Phys Lett 91:149
Bramley MC, Handy NC (1993) J Chem Phys 68:608
Watson JKG (1968) J Mol Spectrosc 15:479
Culot F, Liévin J (1992) Physica Scripta 46:502
Werner HJ, Knowles PJ (1985) J Chem Phys 82:5053
Knowles, PJ, Werner HJ (1985) Chem Phys Lett 115:259
Knowles PJ, Werner HJ (1988) Chem Phys Lett 145:514
Werner HJ, Knowles PJ (1985) J Chem Phys 89:5803
MOLPRO is a package ofab initio programs written by Werner HJ and Knowles PJ, with contributions from Almlöf J, Amos RD, Deegan MJO, Elbert ST, Hampel C, Meyer W, Peterson K, Pitzer R, Stone AJ and Taylor PR
Dunning TH (1988) J Chem Phys 90:1007
Bauschlicher CW, Partridge H (1994) J Chem Phys 100:4329
Rosenberg BJ, Ermler WC, Shavitt I (1976) J Chem Phys 65:4072
Simons G, Parr RG, Finlan JM (1973) J Chem Phys 59:3229
Harding LB, Ermler WC (1985) QCPE Bull 6:25
Le Sueur CR, Miller S, Tennyson J, Sutcliffe BT (1992) Mol Phys 76:1147
Speirs GK, Spirko V (1975) J Mol Spectrosc 56:104
Benedict WS, Gailar N, Plyer EK (1956) J Chem Phys 24:1139
Hoy AR, Mills IM, Strey G (1972) Mol Phys 24:1265
Clough SA, Beers Y, Klein GP, Rothman LS (1973) J Chem Phys 59:2254
Romanovski H, Bowman JM, Harding LB (1985) J Chem Phys 82:4155
Rothman LS, Gamache RR, Tipping RH, Rinsland CP, Smith MAH, Benner DC, Devi VM, Flaud JM, Camy-Peyret C, Perrin A, Goldman A, Massie ST, Brown LR, Toth RA (1992) J Quant Spectrosc Radiat Transfer 48:5556
Bramley MJ, Carter S, Handy NC, Mills IM (1993) J Mol Spectrosc 157:301
Liévin J, Abbouti Temsamani M, Gaspard P, Herman M (1995) Chem Phys 190:419
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Boursier F.R.I.A.
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Culot, F., Laruelle, F. & Liévin, J. A vibrational CASSCF study of stretch-bend interactions and their influence on infrared intensities in the water molecule. Theoret. Chim. Acta 92, 211–226 (1995). https://doi.org/10.1007/BF01125947
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DOI: https://doi.org/10.1007/BF01125947