BENCHMARK CALCULATIONS WITH CORRELATED MOLECULAR WAVE-FUNCTIONS .4. THE CLASSICAL BARRIER HEIGHT OF THE H+H-2-]H-2+H REACTION

被引:1673
作者
PETERSON, KA
WOON, DE
DUNNING, TH
机构
[1] Molecular Science Research Center, Pacific Northwest Laboratory, Richland, WA 99352, P. O. Box
关键词
D O I
10.1063/1.466884
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 systematic sequences of correlation consistent Gaussian basis sets from double to sextuple zeta quality, the classical barrier height of the H+H-2 exchange reaction has been calculated by multireference configuration interaction (MRCI) methods. The MRCI calculations for collinear H-3 have also been calibrated against large basis set full CI (FCI) results, which demonstrate that the MRCI treatment leads to energies less than 1 mu hartree (<0.001 kcal/mol) above the FCI energies. The dependence of both the H-2 and H-3 total energies on the basis set is found to be very regular, and this behavior has been used to extrapolate to the complete basis set (CBS) limits. The resulting estimate of the H-H-H CBS limit yields a classical barrier height, relative to exact H+H-2, of 9.60+/-0.02 kcal/mol; the best directly calculated value for the barrier is equal to 9.62 kcal/mol. These results are in excellent agreement with recent quantum Monte Carlo calculations.
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页码:7410 / 7415
页数:6
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共 36 条
[1]  
ALMLOF J, MOLPRO92 SUITE AB IN
[2]   H + H-2 REACTION BARRIER - A FIXED-NODE QUANTUM MONTE-CARLO STUDY [J].
BARNETT, RN ;
REYNOLDS, PJ ;
LESTER, WA .
JOURNAL OF CHEMICAL PHYSICS, 1985, 82 (06) :2700-2707
[3]   A REEVALUATION OF THE H3-POTENTIAL [J].
BAUSCHLICHER, CW ;
LANGHOFF, SR ;
PARTRIDGE, H .
CHEMICAL PHYSICS LETTERS, 1990, 170 (04) :345-348
[4]   THE H-3 POTENTIAL SURFACE REVISITED [J].
BLOMBERG, MRA ;
LIU, B .
JOURNAL OF CHEMICAL PHYSICS, 1985, 82 (02) :1050-1051
[5]   AN IMPROVED H3 POTENTIAL-ENERGY SURFACE [J].
BOOTHROYD, AI ;
KEOGH, WJ ;
MARTIN, PG ;
PETERSON, MR .
JOURNAL OF CHEMICAL PHYSICS, 1991, 95 (06) :4343-4359
[6]   A NEW SEMI-EMPIRICAL METHOD OF CORRECTING LARGE-SCALE CONFIGURATION-INTERACTION CALCULATIONS FOR INCOMPLETE DYNAMIC CORRELATION OF ELECTRONS [J].
BROWN, FB ;
TRUHLAR, DG .
CHEMICAL PHYSICS LETTERS, 1985, 117 (04) :307-313
[7]   MANY-ELECTRON EXPLICITLY CORRELATED GAUSSIAN FUNCTIONS .1. GENERAL-THEORY AND TEST-RESULTS [J].
CENCEK, W ;
RYCHLEWSKI, J .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (02) :1252-1261
[8]   QUANTUM MONTE-CARLO FOR MOLECULES - GREEN-FUNCTION AND NODAL RELEASE [J].
CEPERLEY, DM ;
ALDER, BJ .
JOURNAL OF CHEMICAL PHYSICS, 1984, 81 (12) :5833-5844
[9]   SELECTED TOPICS IN ABINITIO COMPUTATIONAL CHEMISTRY IN BOTH VERY SMALL AND VERY LARGE CHEMICAL-SYSTEMS [J].
CLEMENTI, E ;
CORONGIU, G ;
BAHATTACHARYA, D ;
FEUSTON, B ;
FRYE, D ;
PREISKORN, A ;
RIZZO, A ;
XUE, W .
CHEMICAL REVIEWS, 1991, 91 (05) :679-699
[10]   AN ACCURATE QUANTUM MONTE-CARLO CALCULATION OF THE BARRIER HEIGHT FOR THE REACTION H+H2-]H2+H [J].
DIEDRICH, DL ;
ANDERSON, JB .
SCIENCE, 1992, 258 (5083) :786-788