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We describe a simplified approach to simulating Raman spectra using ab initio molecular dynamics (AIMD) calculations. Our protocol relies on on-the-fly calculations of approximate molecular polarizabilities using a sum over orbitals (as…

We introduce the Anharmonic Oscillator Symmetry Model to describe vibrational excitations in molecular systems exhibiting high degree of symmetry. A systematic procedure is proposed to establish the relation between the algebraic and…

chem-ph · Physics 2009-10-28 A. Frank , R. Lemus , R. Bijker , F. Perez-Bernal , J. M. Arias

We present a technique for extracting Raman intensities from ab initio molecular dynamics (MD) simulations at high temperature. The method is applied to the highly anharmonic case of dense hydrogen up to 500 K for pressures ranging from 180…

Materials Science · Physics 2013-02-25 Ioan B. Magdau , Graeme J. Ackland

We have developed a formulation of density functional perturbation theory for the calculation of vibrational frequencies in molecules and solids, which uses numerical atomic orbitals as a basis set for the electronic states. The (harmonic)…

Materials Science · Physics 2007-05-23 J. M. Pruneda , S. K. Estreicher , J. Junquera , J. Ferrer , P. Ordejon

Exposing a molecule to intense light pulses may bring this molecule to a nonstationary quantum state, thus launching correlated dynamics of electronic and nuclear subsystems. Although much had been achieved in the understanding of…

Chemical Physics · Physics 2024-04-11 Nikolay V. Golubev , Jiří Vaníček

We undertake a semiclassical analysis of the spectral properties (modulations of photoabsorption spectra, energy level statistics) of a simple Rydberg molecule in static fields within the framework of Closed-Orbit/Periodic-Orbit theories.…

Chaotic Dynamics · Physics 2009-11-07 A. Matzkin , T. S. Monteiro

Both the stretch and bend vibrational spectrum and the intensity of infrared transitions in a tetrahedral molecule are studied in a U(2) algebraic model, where the spurious states in the model Hamiltonian and the wavefunctions are exactly…

Chemical Physics · Physics 2009-10-31 Xi-Wen Hou , Shi-Hai Dong , Mi Xie , Zhong-Qi Ma

When calculating the optical absorption spectra of molecular crystals from first principles, the influence of the crystalline environment on the excitations is of significant importance. For such systems, however, methods to describe the…

Materials Science · Physics 2021-08-17 Joseph C. A. Prentice , Arash A. Mostofi

A general theory of electronic excitations in aggregates of molecules coupled to intramolecular vibrations and the harmonic environment is developed for simulation of the third-order nonlinear spectroscopy signals. The model is applied in…

Chemical Physics · Physics 2014-01-17 Vytautas Butkus , Leonas Valkunas , Darius Abramavicius

Methods for reconstructing the spectral density of a vibrational environment from experimental data can yield key insights into the impact of the environment on molecular function. Although such experimental methods exist, they generally…

Chemical Physics · Physics 2025-09-11 Roosmarijn de Wit , Jonathan Keeling , Brendon W. Lovett , Alex W. Chin

Including quantum mechanical effects on the dynamics of nuclei in the condensed phase is challenging, because the complexity of exact methods grows exponentially with the number of quantum degrees of freedom. Efforts to circumvent these…

Chemical Physics · Physics 2015-06-23 Mariana Rossi , Hanchao Liu , Francesco Paesani , Joel Bowman , Michele Ceriotti

Studying the jamming transition of granular and colloidal systems, has lead to a proliferation of theoretical and numerical results formulated in the language of the eigenspectrum of the dynamical matrix for these disordered system. Only…

Soft Condensed Matter · Physics 2016-01-19 Silke Henkes , Carolina Brito , Olivier Dauchot

Spectroscopy is an indispensable tool in understanding the structures and dynamics of molecular systems. However computational modelling of spectroscopy is challenging due to the exponential scaling of computational complexity with system…

Quantum Physics · Physics 2021-06-22 Chee-Kong Lee , Chang-Yu Hsieh , Shengyu Zhang , Liang Shi

Harmonic inversion techniques have been shown to be a powerful tool for the semiclassical quantization and analysis of quantum spectra of both classically integrable and chaotic dynamical systems. Various computational procedures have been…

Chaotic Dynamics · Physics 2009-11-07 T. Bartsch , J. Main , G. Wunner

Quasicentroid molecular dynamics (QCMD) is a path-integral method for approximating nuclear quantum effects in dynamics simulations, which has given promising results for gas- and condensed-phase water. Here, by simulating the infrared…

Chemical Physics · Physics 2021-11-29 Christopher Haggard , Vijay Ganesh Sadhasivam , George Trenins , Stuart C. Althorpe

With increasing energy the diamagnetic hydrogen atom undergoes a transition from regular to chaotic classical dynamics, and the closed orbits pass through various cascades of bifurcations. Closed orbit theory allows for the semiclassical…

Chaotic Dynamics · Physics 2007-05-23 T. Fabcic , J. Main , T. Bartsch , G. Wunner

Infrared spectroscopy is key to elucidate molecular structures, monitor reactions and observe conformational changes, while providing information on both structural and dynamical properties. This makes the accurate prediction of infrared…

Chemical Physics · Physics 2022-08-30 Richard Beckmann , Fabien Brieuc , Christoph Schran , Dominik Marx

Spectroscopy is a crucial laboratory technique for understanding quantum systems through their interactions with electromagnetic radiation. Particularly, spectroscopy is capable of revealing the physical structure of molecules, leading to…

Quantum Physics · Physics 2018-05-24 Ling Hu , YueChi Ma , Y. Xu , W. Wang , Y. Ma , K. Liu , M. -H. Yung , L. Sun

The transition between the gas-, supercritical-, and liquid-phase behaviour is a fascinating topic which still lacks molecular-level understanding. Recent ultrafast two-dimensional infrared spectroscopy experiments suggested that the…

Chemical Physics · Physics 2023-03-22 Kai Töpfer , Debasish Koner , Shyamsunder Erramilli , Lawrence D. Ziegler , Markus Meuwly

We show how vibronic spectra in molecular systems can be simulated in an efficient and accurate way using first principles approaches without relying on the explicit use of multiple Born-Oppenheimer potential energy surfaces. We demonstrate…

Chemical Physics · Physics 2024-03-01 Kevin Lively , Guillermo Albareda , Shunsuke A. Sato , Aaron Kelly , Angel Rubio