A Lagrangian, integral-density direct formulation and implementation of the analytic CCSD and CCSD(T) gradients

被引:65
作者
Hald, K
Halkier, A
Jorgensen, P
Coriani, S
Hättig, C
Helgaker, T
机构
[1] Aarhus Univ, Dept Chem, DK-8000 Aarhus C, Denmark
[2] Univ Trieste, Dipartimento Sci Chim, I-34127 Trieste, Italy
[3] Forschungszentrum Karlsruhe, Inst Nanotechnol, D-76021 Karlsruhe, Germany
[4] Univ Oslo, Dept Chem, N-0315 Oslo, Norway
关键词
D O I
10.1063/1.1531106
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
Using a Lagrangian formulation an integral-density direct implementation of the analytic CCSD(T) molecular gradient is presented, which circumvents the bottleneck of storing either O(N-4) two-electron integrals or O(N-4) density matrix elements on disk. Canonical orbitals are used to simplify the implementation of the frozen-core approximation and the CCSD gradient is obtained as a special case. Also a new, simplified approach to (geometrical) derivative integrals is presented. As a first application we report a full geometry optimization for the most stable isomer of SiC3 using the cc-pV5Z basis set with 368 contracted basis functions and the frozen-core approximation. (C) 2003 American Institute of Physics.
引用
收藏
页码:2985 / 2998
页数:14
相关论文
共 52 条
[1]  
[Anonymous], MODERN ELECT STRUC 2
[2]  
AZHARY AE, 1993, J CHEM PHYS, V10, P5185
[3]   The accuracy of molecular dipole moments in standard electronic structure calculations [J].
Bak, KL ;
Gauss, J ;
Helgaker, T ;
Jorgensen, P ;
Olsen, J .
CHEMICAL PHYSICS LETTERS, 2000, 319 (5-6) :563-568
[4]   The accurate determination of molecular equilibrium structures [J].
Bak, KL ;
Gauss, J ;
Jorgensen, P ;
Olsen, J ;
Helgaker, T ;
Stanton, JF .
JOURNAL OF CHEMICAL PHYSICS, 2001, 114 (15) :6548-6556
[5]   Accuracy of atomization energies and reaction enthalpies in standard and extrapolated electronic wave function/basis set calculations [J].
Bak, KL ;
Jorgensen, P ;
Olsen, J ;
Helgaker, T ;
Klopper, W .
JOURNAL OF CHEMICAL PHYSICS, 2000, 112 (21) :9229-9242
[6]   NONITERATIVE 5TH-ORDER TRIPLE AND QUADRUPLE EXCITATION-ENERGY CORRECTIONS IN CORRELATED METHODS [J].
BARTLETT, RJ ;
WATTS, JD ;
KUCHARSKI, SA ;
NOGA, J .
CHEMICAL PHYSICS LETTERS, 1990, 165 (06) :513-522
[7]   Large-scale calculations of excitation energies in coupled cluster theory: The singlet excited states of benzene [J].
Christiansen, O ;
Koch, H ;
Halkier, A ;
Jorgensen, P ;
Helgaker, T ;
deMeras, AS .
JOURNAL OF CHEMICAL PHYSICS, 1996, 105 (16) :6921-6939
[8]   On the molecular electric quadrupole moment and the electric-field-gradient-induced birefringence of CO2 and CS2 [J].
Coriani, S ;
Halkier, A ;
Rizzo, A ;
Ruud, K .
CHEMICAL PHYSICS LETTERS, 2000, 326 (3-4) :269-276
[9]  
Dunning T. H., 1998, Encyclopedia of Computational Chemistry, P88
[10]   A road map for the calculation of molecular binding energies [J].
Dunning, TH .
JOURNAL OF PHYSICAL CHEMISTRY A, 2000, 104 (40) :9062-9080