Optimized Structure and Vibrational Properties by Error Affected Potential Energy Surfaces

被引:22
作者
Zen, Andrea [2 ]
Zhelyazov, Delyan [3 ]
Guidoni, Leonardo [1 ]
机构
[1] Univ Aquila, Dipartimento Sci Fis & Chim, I-67100 Laquila, Italy
[2] Univ Roma La Sapienza, Dipartimento Fis, I-00185 Rome, Italy
[3] Univ Aquila, Dipartimento Matemat Pura & Applicata, I-67100 Laquila, Italy
基金
欧洲研究理事会;
关键词
QUANTUM MONTE-CARLO; ANHARMONIC-FORCE FIELDS; DENSITY-FUNCTIONAL THEORY; HIGHER-DERIVATIVE METHODS; AB-INITIO CALCULATION; POLYATOMIC-MOLECULES; WAVE-FUNCTIONS; ROTATION INTERACTION; PERTURBATION-THEORY; MOLLER-PLESSET;
D O I
10.1021/ct300576n
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 precise theoretical determination of the geometrical parameters of molecules at the minima of their potential energy surface and of the corresponding vibrational properties are of fundamental importance for the interpretation of vibrational spectroscopy experiments. Quantum Monte Carlo techniques are correlated electronic structure methods promising for large molecules,: which are intrinsically affected by stochastic errors on both energy and force calculations, making the mentioned calculations more challenging with respect to other more traditional quantum chemistry tools. To circumvent this drawback in the present work, we formulate the general problem of evaluating the molecular equilibrium structures, the harmonic frequencies, and the anharmonic coefficients of an error affected potential energy surface. The proposed approach, based on a multidimensional fitting procedure, is illustrated together with a critical evaluation of systematic and statistical errors. We observe that the use of forces, instead of energies in the fitting procedure reduces the statistical uncertainty of the vibrational parameters by 1 order of magnitude. Preliminary results based on variational Monte Carlo calculations on the water molecule demonstrate the possibility to evaluate geometrical parameters and harmonic and anharmonic coefficients at this level of theory with an affordable computational Cost and a small stochastic uncertainty (<0.07% for geometries and <0.7% for vibrational properties).
引用
收藏
页码:4204 / 4215
页数:12
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