Summary
This paper reports a series of coupled-cluster (CC) calculations through CCSDT on the theoretically challenging ground state of the BeO molecule. Along with CC methods, quadratic configuration interaction (QCI) approximations to CC theory have been used (QCISD and QCISD(T)), which show several dramatic failings. Equilibrium electrical properties (μ, α xx , and α zz ) and basic spectroscopic properties (r e, θe,D e, and infrared intensity (I)) have been computed. Basis set and electron correlation effects are analyzed in order to arrive at accurate values of the dipole moment and polarizability, which are not known experimentally. For the dipole moment, we obtain a value of 6.25 D, with an uncertainty of about 0.1 D. For α xx and α zz , we suggest respective values of 32 and 36 atomic units (a.u.) and error bars of about 1 and 2 a.u. With extended basis sets, the spectroscopic propertiesr e, θe, andD e are reproduced to high accuracy, which is the first time this has been achieved for this species byab initio methods. At the highest calculation levels,I is predicted to be very small. AlthoughI has not been measured, some support for this prediction comes from a recent infrared study of BeO-rare gas complexes. The QCI methods are shown to be much more sensitive to basis set, and even with large basis sets yield values of α zz andI which differ from CC results by an order of magnitude and three orders of magnitude, respectively. These differences doubtless arise from the importance of single excitations (T 1) for this molecule, as several terms involvingT 1 are neglected in the QCISD approximation compared with CCSD. We also report CC calculations with Brueckner orbitals, which yield results similar to those obtained with restricted Hartree-Fock orbitals.
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References
Schaefer HF III (1971) J Chem Phys 55:176
Koch W, Collins JR, Frenking G (1986) Chem Phys Lett 132:330; Koch W, Frenking G, Gauss J, Cremer D, Collins JR (1987) J Am Chem Soc 109:5917
Frenking G, Koch W, Gauss J, Cremer D (1988) J Am Chem Soc 110:8007
Frenking G, Koch W, Collins JR (1988) J Chem Soc Chem Commun 1147
Adamowicz L, Bartlett RJ (1985) J Chem Phys 83:6268
Thompson CA, Andrews L (1994) J Am Chem Soc 116:423
Yoshimine M (1964) J Chem Phys 40:2970; Verhaegen G, Richards WG (1966) J Chem Phys 45:1828; Huo WM, Freed KF, Klemperer W (1967) J Chem Phys 46:3556
Yoshimine M (1968) J Phys Soc Jpn 25:1100
O'Neil SV, Pearson PK, Schaefer III HF (1971) Chem Phys Lett 10:404; Pearson PK, O'Neil SV, Schaefer III HF (1972) J Chem Phys 56:3938
Langhoff SR, Bauschlicher Jr CW, Partridge H (1986) J Chem Phys 84:4474
Scuseria GE, Hamilton TP, Schaefer III HF (1990) J Chem Phys 92:568
Irisawa J, Iwata S (1992) Theor Chim Acta 81:223
Yoshioka Y, Jordan KD (1980) J Chem Phys 73:5899; Chem Phys 56:303
Pyykko P, Sundholm D, Laaksonen L (1987) Mol Phys 60:597
Diercksen GHF, Sadlej AJ, Urban M (1991) Chem Phys 158:19
Galasso V (1983) J Mol Struct (THEOCHEM) 10:201
Bauschlicher Jr CW, Langhoff SR (1988) Theor Chim Acta 73:43
Bauschicher Jr CW, Yarkony DR (1980) J Chem Phys 72:1138; Bauchlicher Jr CW Lengsfield III BH, Yarkony DR (1980) J Chem Phys 73:5702
Bauschlicher Jr CW, Bagus PS, Yarkony DR, Lengsfield III BH (1981) J Chem Phys 74:3965; Werner H-J, Meyer W (1981) J Chem Phys 74:5794; Golab JT, Yeager DL, Jörgensen P (1983) Chem Phys Lett 78:175
Chang KJ, Cohen ML (1984) Solid State Commun 50:487; Brey L, Christensen NE, Cardona M (1987) Phys Rev B 36:2638
Chiles RA, Dykstra CE (1981) J Chem Phys 74:4544
Handy NC, Pople JA, Head-Gordon M, Raghavachari K, Trucks GW (1989) Chem Phys Lett 164:185
Stanton JF, Gauss J, Bartlett RJ (1992) J Chem Phys 97:5554
Lee TJ, Rice JE, Scuseria GE, Schaefer III HF (1989) Theor Chim Acta 75:81
Lee TJ, Taylor PR (1989) Int J Quantum Chem Symp 23:199
Dunning Jr TH, Hay PJ (1977) in Schaefer III HF (ed), Methods of electronic structure theory, Plenum, New York
Dunning Jr TH (1970) J Chem Phys 53:2823
Sadlej AJ (1988) Collec Czech Chem Commun 53:1995; Sadlej AJ, Urban M (1991) J Mol Struct (THEOCHEM) 234:147
Frisch MJ, Pople JA, Binkley JS (1984) J Chem Phys 80:3265
Widmark PO, Malmqvist PA, Roos BO (1990) Theor Chim Acta 77:291
ACES II is a quantum chemical program package especially designed for CC and MBPT energy and gradient calculations. Elements of this package are: the SCF, integral transformation, correlation energy, and gradient codes written by Stanton JF, Gauss J, Watts JD, Lauderdale WJ, Bartlett RJ, the VMOL integral and VPROPS property integral programs written by Taylor PR and Almlöf J, a modified version of the integral derivative program ABACUS written by Helgaker T, Aa Jensen HJ, Jørgensen P, Olsen J, Taylor PR
Huber KP, Herzberg G (1979) Constants of diatomic molecules, Van Nostrand Reinhold, New York
Stanton JF, Gauss JD, Watts J, Lauderdale WJ, Bartlett RJ (1992) Int J Quantum Chem Symp 26:879 and references therein; Watts J, Gauss JD, Bartlett RJ (1992) Chem Phys Lett 200:1; Watts JD, Gauss J, Bartlett RJ (1993) J Chem Phys 98:8718
Purvis III GD, Bartlett RJ (1982) J Chem Phys 76:1910
Noga J, Bartlett RJ (1987) J Chem Phys 88:7041
Lee YS, Kucharski SA, Bartlett RJ (1984) J Chem Phys 81:5906
Urban M, Noga J, Cole SJ, Bartlett RJ (1985) J Chem Phys 83:4041
Noga J, Bartlett RJ, Urban M (1987) Chem Phys Lett 134:126
Raghavachari K, Trucks GW, Pople JA, Head-Gordon M (1985) Chem Phys Lett 157:479
Bartlett RJ, Watts JD, Kucharski SA, Noga J (1990) Chem Phys Lett 165:513
Pople JA, Head-Gordon M, Raghavachari K (1987) J Chem Phys 87:5968
Laidig WD, Purvis III GD, Bartlett RJ (1982) Int J Quantum Chem Symp 6:561
Laidig WD, Purvis III GD, Bartlett RJ (1983) Chem Phys Lett 97:209
Laidig WD, Purvis III GD, Bartlett RJ (1985) J Phys Chem 89:2161
Adamowicz L, Bartlett RJ (1986) Int J Quantum Chem Symp 19:217
Lee TJ, Rendell AP, Taylor PR (1990) J Phys Chem 94:5463
Martin JML, Taylor PR (1994) J Chem Phys 100:9002
Scuseria GE, Lee TJ (1990) J Chem Phys 93:5851
Bowman JM, Gazdy B, Bentley JA, Lee TJ, Dateo CE (1993) J Chem Phys 99:308
Bartlett RJ, Purvis III GD (1978) Int J Quantum Chem Symp 14:561
Watts JD, Bartlett RJ (1992) J Chem Phys 96:6073
Martin JML, Lee TJ, Scuseria GE, Taylor PR (1992) J Chem Phys 97:6549
Watts JD, Bartlett RJ (1994) Int J Quantum Chem Symp 28:195
Bartlett RJ (1989) J Phys Chem 93:1697
Bartlett RJ, Stanton JF (1994) in (eds) Review in computational chemistry, Lipkowitz KB, Boyd DB Vol. V, pp 65–169, VCH Publishers, New York
Kobayashi R, Koch H, Jørgensen P, Lee TJ (1993) Chem Phys Lett 211:94
Lee TJ, Kobayashi R, Handy NC, Amos RD (1992) J Chem Phys 96:8931
Rico RJ, Head-Gordon M (1993) Chem Phys Lett 213:224
Comeau DC, Bartlett RJ (1993) Chem Phys Lett 207:414
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Watts, J.D., Urban, M. & Bartlett, R.J. Accurate electrical and spectroscopic properties ofX 1Σ+ BeO from coupled-cluster methods. Theoret. Chim. Acta 90, 341–355 (1995). https://doi.org/10.1007/BF01113541
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DOI: https://doi.org/10.1007/BF01113541