Accurate Open-Shell Noncovalent Interaction Energies from the Orbital-Optimized Moller-Plesset Perturbation Theory: Achieving CCSD Quality at the MP2 Level by Orbital Optimization

被引:30
作者
Soydas, Emine [1 ]
Bozkaya, Ugur [1 ]
机构
[1] Ataturk Univ, Dept Chem, TR-25240 Erzurum, Turkey
关键词
CORRELATED MOLECULAR CALCULATIONS; COUPLED-CLUSTER THEORY; BASIS-SET CONVERGENCE; GAUSSIAN-BASIS SETS; SYMMETRY-BREAKING; SPIN-COMPONENT; HARTREE-FOCK; DOUBLES MODEL; SINGLE; SEQUENCES;
D O I
10.1021/ct4008124
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
The accurate description of noncovalent interactions is one of the most challenging problems in modern computational chemistry, especially those for open-shell systems. In this study, an investigation of open-shell noncovalent interactions with the orbital-optimized MP2 and MP3 (OMP2 and OMP3) is presented. For the considered test set of 23 complexes, mean absolute errors in noncovalent interaction energies (with respect to CCSD(T) at complete basis set limits) are 0.68 (MP2), 0.37 (OMP2), 0.59 (MP3), 0.23 (OMP3), and 0.38 (CCSD) kcal mol(-1). Hence, with a greatly reduced computational cost, one may achieve CCSD quality at the MP2 level by orbital optimization [scaling formally as O(N-6) for CCSD compared to O(N-5) for OMP2, where N is the number of basis functions]. Further, one may obtain a considerably better performance than CCSD using the OMP3 method, which has also a lower cost than CCSD.
引用
收藏
页码:4679 / 4683
页数:5
相关论文
共 75 条
[1]   THE LITHIUM SUPEROXIDE RADICAL - SYMMETRY-BREAKING PHENOMENA AND POTENTIAL-ENERGY SURFACES [J].
ALLEN, WD ;
HORNER, DA ;
DEKOCK, RL ;
REMINGTON, RB ;
SCHAEFER, HF .
CHEMICAL PHYSICS, 1989, 133 (01) :11-45
[2]   A nonorthogonal CI treatment of symmetry breaking in sigma formyloxyl radical [J].
Ayala, PY ;
Schlegel, HB .
JOURNAL OF CHEMICAL PHYSICS, 1998, 108 (18) :7560-7567
[3]   Potential energy surface for the hydroperoxy and water (HO2•H2O) radical complex [J].
Belair, SD ;
Kais, S ;
Francisco, JS .
MOLECULAR PHYSICS, 2002, 100 (02) :247-253
[4]   CALCULATION OF SMALL MOLECULAR INTERACTIONS BY DIFFERENCES OF SEPARATE TOTAL ENERGIES - SOME PROCEDURES WITH REDUCED ERRORS [J].
BOYS, SF ;
BERNARDI, F .
MOLECULAR PHYSICS, 1970, 19 (04) :553-&
[5]   The extended Koopmans' theorem for orbital-optimized methods: Accurate computation of ionization potentials [J].
Bozkaya, Ugur .
JOURNAL OF CHEMICAL PHYSICS, 2013, 139 (15)
[6]   Analytic energy gradients for the orbital-optimized third-order Moller-Plesset perturbation theory [J].
Bozkaya, Ugur .
JOURNAL OF CHEMICAL PHYSICS, 2013, 139 (10)
[7]   Orbital-optimized coupled-electron pair theory and its analytic gradients: Accurate equilibrium geometries, harmonic vibrational frequencies, and hydrogen transfer reactions [J].
Bozkaya, Ugur ;
Sherrill, C. David .
JOURNAL OF CHEMICAL PHYSICS, 2013, 139 (05)
[8]   Analytic energy gradients for the orbital-optimized second-order Moller-Plesset perturbation theory [J].
Bozkaya, Ugur ;
Sherrill, C. David .
JOURNAL OF CHEMICAL PHYSICS, 2013, 138 (18)
[9]   Symmetric and asymmetric triple excitation corrections for the orbital-optimized coupled-cluster doubles method: Improving upon CCSD(T) and CCSD(T)Λ: Preliminary application [J].
Bozkaya, Ugur ;
Schaefer, Henry F., III .
JOURNAL OF CHEMICAL PHYSICS, 2012, 136 (20)
[10]   The lowest-lying electronic singlet and triplet potential energy surfaces for the HNO-NOH system: Energetics, unimolecular rate constants, tunneling and kinetic isotope effects for the isomerization and dissociation reactions [J].
Bozkaya, Ugur ;
Turney, Justin M. ;
Yamaguchi, Yukio ;
Schaefer, Henry F., III .
JOURNAL OF CHEMICAL PHYSICS, 2012, 136 (16)