A benchmark study of molecular structure by experimental and theoretical methods: Equilibrium structure of thymine from microwave rotational constants and coupled-cluster computations

被引:12
|
作者
Vogt, Natalja [1 ,2 ]
Demaison, Jean [1 ]
Ksenafontov, Denis N. [2 ]
Rudolph, Heinz Dieter [1 ]
机构
[1] Univ Ulm, D-89069 Ulm, Germany
[2] Moscow MV Lomonosov State Univ, Dept Chem, Moscow 119992, Russia
关键词
Equilibrium rotational constants; Semi-experimental structure; Predicate bond parameters; Mixed estimation method; Anharmonic rovibrational corrections; Thymine; PHASE ELECTRON-DIFFRACTION; GAS-PHASE; BASIS-SETS; AB-INITIO; ATOMS; SUBSTITUTION; SPECTRA; DENSITY; URACIL;
D O I
10.1016/j.molstruc.2014.08.004
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
Accurate equilibrium, r(e), structures of thymine have been determined using two different, and to some extent complementary techniques. The composite ab initio Born-Oppenheimer, r(e)(best ab initio), structural parameters are obtained from the all-electron CCSD(T) and MP2 geometry optimizations using Gaussian basis sets up to quadruple-zeta quality. The semi-experimental mixed estimation method, where internal coordinates are fitted concurrently to equilibrium rotational constants and geometry parameters obtained from a high level of electronic structure theory. The equilibrium rotational constants are derived from experimental effective ground-state rotational constants and rovibrational corrections based on a quantum-chemical cubic force field. Equilibrium molecular structures accurate to 0.002 angstrom and 0.2 degrees have been determined. This work is one of a few accurate equilibrium structure determinations for large molecules. The poor behavior of Kraitchman's equations is discussed. (C) 2014 Elsevier B.V. All rights reserved.
引用
收藏
页码:483 / 489
页数:7
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