Tunneling splitting in vibrational spectra of non-rigid molecules. II. Excited states

Benderskiĭ, V. A.; Vetoshkin, E. V.; Laue, L. von; Trommsdorff, H.P.

doi:10.1016/s0301-0104(97)00119-5

Cited by 46 publications

(22 citation statements)

References 28 publications

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“…When the β L¯v alue is larger than 60, two methods give the same converged result, which means that b L 0 numerically equals b ∞ , see Eqs. (13) and (25). In fact, b m converges very fast regarding m, see Eq.…”

Section: Numerical Application To a One-dimensional Systemmentioning

confidence: 92%

“…[15][16][17][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] In the present paper, we focus a method using the discretized imaginary time approach developed by Richardson and Althorpe, because their method is constructed on the basis of the standard path integral molecular simulation technology, which facilitates the reuse of existing computational libraries on the path integrals. 41,42 Then, the single kink path is computed by minimizing the potential energy of isomorphic polymers with a proper boundary condition.…”

Section: Introductionmentioning

confidence: 99%

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Efficient algorithms for semiclassical instanton calculations based on discretized path integrals

Kawatsu

Miura

2014

The Journal of Chemical Physics

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A calculation of the rovibronic energies and spectrum of the B A 1 1 electronic state of Si H 2 J. Chem. Phys. 123, 244312 (2005) Path integral instanton method is a promising way to calculate the tunneling splitting of energies for degenerated two state systems. In order to calculate the tunneling splitting, we need to take the zero temperature limit, or the limit of infinite imaginary time duration. In the method developed by Richardson and Althorpe [J. Chem. Phys. 134, 054109 (2011)], the limit is simply replaced by the sufficiently long imaginary time. In the present study, we have developed a new formula of the tunneling splitting based on the discretized path integrals to take the limit analytically. We have applied our new formula to model systems, and found that this approach can significantly reduce the computational cost and gain the numerical accuracy. We then developed the method combined with the electronic structure calculations to obtain the accurate interatomic potential on the fly. We present an application of our ab initio instanton method to the ammonia umbrella flip motion. © 2014 AIP Publishing LLC.[http://dx

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Section: Numerical Application To a One-dimensional Systemmentioning

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Efficient algorithms for semiclassical instanton calculations based on discretized path integrals

Kawatsu

Miura

2014

The Journal of Chemical Physics

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“…In this description CH 3 Cl represents a ferro-orientational structure. Due to the molecular symmetry there is no intramolecular hindering potential and the methyl rotation is identical to the rotation of the whole molecule around its symmetry axis.…”

Section: A Crystal Structuresmentioning

confidence: 99%

“…The group of the methyl halides is interesting because they can be used to check hydrogen-halide interatomic pair potentials by consistently describing the lattice dynamics and rotational tunneling of CH 3 groups. Since all of the crystal structures are known, a systematic study of this class of molecules is possible.…”

Section: Introductionmentioning

confidence: 99%

The lattice and rotational dynamics of the methyl halides described by pair potentials based on universal force fields

Kirstein

Prager

2004

The Journal of Chemical Physics

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A systematical computational study of the lattice and rotational dynamics of the methyl halides, which belong to the most simple organic molecules containing CH 3 groups, was done. Because of their simplicity there might be a chance to understand and model the dynamics of these systems by combining nonbonded pair interactions and crystallographic information. Based on the experimentally determined crystal structure, which was not relaxed during the calculations, interactions were modeled using the transferable parameters of the universal force fields. The lattice dynamical calculation can reproduce with reasonable accuracy the low-energy regime of the lattice excitations as well as the single-particle rotational potential of the CH 3 group of the respective halide.

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“…Tunneling proton dynamics in metal hydrides (66) is of practical importance in fuel cell applications, whereas tunneling along hydrogen bonds (67,68) is of fundamental importance in the proton transfer reactions that are ubiquitous in physical and life sciences. In this latter case, proton tunneling mediates a chemical reaction (69), and proton displacements are smaller (∼0.5Å) than in rotational problems, but the potential barriers can be very strong (∼0.5 eV) and soft molecular vibrations participate in the tunneling dynamics; a one-dimensional dynamical model is not sufficient (70). It is an ongoing challenge for experimentalists and computational chemists to elucidate and quantify the role of molecular vibrations in proton transfer.…”

Section: Perspectivesmentioning

confidence: 99%

Quantitative Atom-Atom Potentials from Rotational Tunneling: Their Extraction and Their Use

Johnson

Kearley

2000

Annu. Rev. Phys. Chem.

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Key Words tunneling, force fields, quantum chemistry, neutron scattering s Abstract Rotational tunneling of small molecular groups has been the subject of considerable theoretical and experimental activity for several decades. Much of this activity has been driven by the promise of exploiting the extreme sensitivity of quantum tunneling to interatomic potentials, but until recently, there was no straightforward means by which quantitative information about these potentials could be extracted. This review explains how a quantitative method, suitable for general application, was developed. It then goes on to show how this has been used to understand tunneling systems for which no previous satisfactory explanation had been found. The application of the methodology, and its results, to other disciplines is discussed.

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Tunneling splitting in vibrational spectra of non-rigid molecules. II. Excited states

Cited by 46 publications

References 28 publications

Efficient algorithms for semiclassical instanton calculations based on discretized path integrals

Efficient algorithms for semiclassical instanton calculations based on discretized path integrals

The lattice and rotational dynamics of the methyl halides described by pair potentials based on universal force fields

Quantitative Atom-Atom Potentials from Rotational Tunneling: Their Extraction and Their Use

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