TOTALLY DRESSED SDCI CALCULATIONS - AN APPLICATION TO HF AND F2

被引:4
作者
SANCHEZMARIN, J [1 ]
NEBOTGIL, I [1 ]
MAYNAU, D [1 ]
MALRIEU, JP [1 ]
机构
[1] UNIV TOULOUSE 3,PHYS QUANT LAB,F-31062 TOULOUSE,FRANCE
来源
THEORETICA CHIMICA ACTA | 1995年 / 92卷 / 04期
关键词
INTERMEDIATE HAMILTONIANS; TOTAL DRESSING; SIZE-CONSISTENT CONFIGURATION INTERACTIONS; LINKED AND UNLINKED DIAGRAMS; SPECTROSCOPIC CONSTANTS;
D O I
10.1007/s002140050124
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A previously proposed procedure including the linked and unlinked contributions due to Triple and Quadruple excitations into a size-consistent SDCI-like model has been applied to HF and F-2 single-bond systems. The procedure is a non-iterative approximation to the more general total dressing model, which is based on the intermediate Hamiltonians theory. Three basis sets have been employed: the correlation consistent cc-pVTZ basis, a similar one including 3d1f polarization functions, and another including one set of g polarization functions. Excellent agreement with experiment and high-quality calculations is obtained for both equilibrium distances and spectroscopic constants. The possibilities of the method in treating single-bond breaking are also demonstrated. Finally, the Linked and Non-Linked contributions from Triple and Quadruple excitations are analysed separately and it is suggested that the addition of the linked triples to the size-consistent SDCI is sufficient to have quantitatively correct spectroscopic properties in going from the size-consistent SDCI to nearly experimental values.
引用
收藏
页码:241 / 252
页数:12
相关论文
共 41 条
[1]   THE IMPACT OF HIGHER POLARIZATION BASIS FUNCTIONS ON MOLECULAR AB-INITIO RESULTS .2. THE GROUND-STATES OF CO, N-2 NO, O-2, AND F2 [J].
AHLRICHS, R ;
SCHARF, P ;
JANKOWSKI, K .
CHEMICAL PHYSICS, 1985, 98 (03) :381-386
[2]  
BARTLETT RJ, 1994, REV COMP CH, V5, P65, DOI 10.1002/9780470125823.ch2
[3]   BENCHMARK FULL CONFIGURATION-INTERACTION CALCULATIONS ON HF AND NH2 [J].
BAUSCHLICHER, CW ;
LANGHOFF, SR ;
TAYLOR, PR ;
HANDY, NC ;
KNOWLES, PJ .
JOURNAL OF CHEMICAL PHYSICS, 1986, 85 (03) :1469-1474
[4]  
BINKLEY JS, 1983, INT J QUANTUM CHEM S, V17, P331
[5]   SIZE-CONSISTENT SELF-CONSISTENT TRUNCATED OR SELECTED CONFIGURATION-INTERACTION [J].
DAUDEY, JP ;
HEULLY, JL ;
MALRIEU, JP .
JOURNAL OF CHEMICAL PHYSICS, 1993, 99 (02) :1240-1254
[8]   VIBRATIONAL FREQUENCY-SHIFTS IN HYDROGEN-BONDED SYSTEMS - THE HYDROGEN-FLUORIDE DIMER AND TRIMER [J].
GAW, JF ;
YAMAGUCHI, Y ;
VINCENT, MA ;
SCHAEFER, HF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (11) :3133-3138
[9]   THE TRIFLUORIDE ANION - A DIFFICULT CHALLENGE FOR QUANTUM-CHEMISTRY [J].
HEARD, GL ;
MARSDEN, CJ ;
SCUSERIA, GE .
JOURNAL OF PHYSICAL CHEMISTRY, 1992, 96 (11) :4359-4366
[10]   4 SELF-CONSISTENT DRESSINGS TO ACHIEVE SIZE-CONSISTENCY OF SINGLES AND DOUBLES CONFIGURATION-INTERACTION [J].
HEULLY, JL ;
MALRIEU, JP .
CHEMICAL PHYSICS LETTERS, 1992, 199 (06) :545-550