A systematic study of molecular vibrational anharmonicity and vibration-rotation interaction by self-consistent-field higher-derivative methods. Linear polyatomic molecules

Allen, Wesley D.; Yamaguchi, Yukio; Császár, Attila G.; Clabo, D. Allen; Remington, Richard B.; Schaefer, Henry F.

doi:10.1016/0301-0104(90)87051-c

Cited by 270 publications

(156 citation statements)

References 97 publications

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“…As a consequence of this, the linear coefficients F i in the expansion cannot be assumed equal to zero any more; in fact, they will be as small as is close to . Therefore, we obtain the equation: (24) that is linearly parametrized by and functionally depends on the displacement from the guess configuration.…”

Section: Multidimensional Fit Of Pesmentioning

confidence: 99%

Optimized Structure and Vibrational Properties by Error Affected Potential Energy Surfaces

Zen

Zhelyazov

Guidoni

2012

J. Chem. Theory Comput.

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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).

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Section: Multidimensional Fit Of Pesmentioning

confidence: 99%

Optimized Structure and Vibrational Properties by Error Affected Potential Energy Surfaces

Zen

Zhelyazov

Guidoni

2012

J. Chem. Theory Comput.

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“…74 The ab initio structure and the anharmonic force field of N 2 O has been calculated repeatedly. [75][76][77][78] In this study, estimates of the r e BO structure of N 2 O have been computed at the MP2 and CCSD(T) levels ( Table 7). The coupled-cluster T 1 diagnostic is 0.0198 at the VQZ CCSD(T) level, slightly larger than for FNO 2 , but slightly smaller than that for HONO and FNO.…”

Section: Equilibrium Structures Of Nitrous Oxide N 2 Omentioning

confidence: 99%

The Case of the Weak N−X Bond: Ab Initio, Semi-Experimental, and Experimental Equilibrium Structures of XNO (X = H, F, Cl, OH) and FNO₂

2006

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The equilibrium structures of FNO, ClNO, HONO, and FNO 2 have been determined using three different, somewhat complementary methods: a completely experimental, a semi-experimental (where the equilibrium rotational constants are derived from the experimental effective ground-state rotational constants and an ab initio cubic force field), and an ab initio, where geometry optimizations are usually performed at the coupled cluster level of nonrelativistic electronic structure theory using small to very large Gaussian basis sets. For the sake of comparison, the equilibrium structures of HNO and N 2 O have also been redetermined, confirming and extending earlier results. The semi-experimental method gives structural parameters in good agreement with the reliable experimental results for each compound investigated. Because of inadequate treatment of electron correlation, the single-reference CCSD(T) method gives N-X (XdF, Cl, OH) bonds that are too strong and associate bond lengths that are significantly too short. The discrepancy increases with increase in the size of the basis set. A much more elaborate treatment of electron correlation at the CCSDTQ level solves this problem and results in increased bond lengths, correctly representing the weakness of the N-X bond in these XNO and XNO 2 species. The equilibrium structures determined are accurate to better than 0.001 Å and 0.1°.

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“…These are sufficient for second-order rovibrational perturbation theory analyses [36,37,38,39,40], which were carried out using the SPECTRO [41] and POLYAD [42] programs developed in the Cambridge group and at Weizmann, respectively.…”

Section: Computational Detailsmentioning

confidence: 99%

Vibrational Spectra of the Azabenzenes Revisited: Anharmonic Force Fields

2003

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Anharmonic force fields and vibrational spectra of the azabenzene series (pyridine, pyridazine, pyrimidine, pyrazine, s-triazine, 1,2,3-triazine, 1,2,4-triazine and s-tetrazine) and benzene are obtained using density functional theory (DFT) with the B97-1 exchange-correlation functional and a triple-zeta plus double polarization (TZ2P) basis set. Overall, the fundamental frequencies computed by second-order rovibrational perturbation theory are in excellent agreement with experiment. The resolution of the presently calculated anharmonic spectra is such that they represent an extremely useful tool for the assignment and interpretation of the experimental spectra, especially where resonances are involved.

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A systematic study of molecular vibrational anharmonicity and vibration-rotation interaction by self-consistent-field higher-derivative methods. Linear polyatomic molecules

Cited by 270 publications

References 97 publications

Optimized Structure and Vibrational Properties by Error Affected Potential Energy Surfaces

Optimized Structure and Vibrational Properties by Error Affected Potential Energy Surfaces

The Case of the Weak N−X Bond: Ab Initio, Semi-Experimental, and Experimental Equilibrium Structures of XNO (X = H, F, Cl, OH) and FNO₂

Vibrational Spectra of the Azabenzenes Revisited: Anharmonic Force Fields

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A systematic study of molecular vibrational anharmonicity and vibration-rotation interaction by self-consistent-field higher-derivative methods. Linear polyatomic molecules

Cited by 270 publications

References 97 publications

Optimized Structure and Vibrational Properties by Error Affected Potential Energy Surfaces

Optimized Structure and Vibrational Properties by Error Affected Potential Energy Surfaces

The Case of the Weak N−X Bond: Ab Initio, Semi-Experimental, and Experimental Equilibrium Structures of XNO (X = H, F, Cl, OH) and FNO2

Vibrational Spectra of the Azabenzenes Revisited: Anharmonic Force Fields

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The Case of the Weak N−X Bond: Ab Initio, Semi-Experimental, and Experimental Equilibrium Structures of XNO (X = H, F, Cl, OH) and FNO₂