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Srihari Keshavamurthy

Publications and source records attributed to Srihari Keshavamurthy.

At least 19 recordsLinked to original sources
arXiv2026

Vibrational strong coupling influences product selectivity in a model for post transition state bifurcation reactions

Understanding the mechanism of chemical reaction rate modulation by vibrational strong coupling (VSC) has been the focus of several recent studies. However, a definitive explanation for the mode-specificity of VSC still eludes us. In this study, we highlight the dynamics under VSC by utilizing a model for post-transition state bifurcation (PTSB) reactions coupled to an optical cavity. The minimal two-dimensional PTSB model features a valley-ridge inflection (VRI) point leading to bifurcated energetically asymmetric product wells. Here, we are interested in exploring whether the product selectivity (branching ratios) in such PTSB systems, known to be sensitive to dynamical effects, can be significantly perturbed under VSC conditions. Detailed classical and quantum dynamical calculations, along with systematic variation of the model parameters, reveals that the branching ratio can be enhanced under VSC by nearly a factor of two. Interestingly, for certain parameter regimes we find excellent classical-quantum correspondence. Apart from emphasizing the role of both cavity-system and intramolecular energy transfer in the observed enhancements, our study brings out the complexity of VSC in terms of the choice of the cavity frequency vis--à--vis the various molecular mode frequencies. In addition, our work highlights the potential of cavity quantum electrodynamics as a tool for reshaping dynamical outcomes in reactions with complex potential energy landscapes.

physics.chem-ph↗
arXiv2022

Dissociation dynamics of a diatomic molecule in an optical cavity

We study the dissociation dynamics of a diatomic molecule, modeled as a Morse oscillator, coupled to an optical cavity. In both classical and quantum dynamics simulations, a marked suppression of the dissociation probability is observed for cavity frequencies significantly below the fundamental transition frequency of the molecule. We show that the suppression in the probability occurs when certain key nonlinear resonances in the classical phase space of the molecule disappear, possible only when the dipole function is nonlinear. This study demonstrates the complexity of cavity-molecule vibrational energy transfer in the anharmonic limit and suggests further studies are necessary to understand resonance effects in experiments of vibrational polariton chemistry.

physics.chem-ph↗
arXiv2021

Arnold web and dynamical tunneling in a four-site Bose-Hubbard model

We present the quantum and classical study of a four-well trapped Bose-Einstein condensate (BEC) modeled by the Bose-Hubbard Hamiltonian. The model used is fashioned as a minimal bipartite system consisting of a trimer coupled weakly to a monomer. Semiclassical insights into the fragmentation dynamics of the condensate is obtained by mapping out the Arnold web of the high dimensional classical phase space. A remarkable one-to-one correspondence between the quantum state space in occupation number representation and the classical Arnold web in action space is observed. The relevance of dynamical tunneling for the dynamics of Fock states near resonance junctions on the Arnold web is highlighted. We also predict the possibility of manipulating the transport within the trimer subsystem due to the weak coupling to the monomer.

nlin.CD↗
arXiv2021

Influence of low frequency modes on dynamical concertedness in double proton transfer dynamics

We analyze the classical phase space dynamics of a three degree of freedom Hamiltonian that models multiple bond breaking and forming reactions. The model Hamiltonian, inspired from studies on double proton transfer reactions, allows for exploring the dynamical consequences of higher index saddles on multidimensional potential energy surfaces. Studies have shown that coupling of low frequency transverse modes to the reaction coordinate can significantly influence the reaction mechanism, concerted or sequential, as inferred from a reduced dimensional analysis. Using the notion of dynamically concerted and sequential pathways, we provide insights into the role of the transverse modes by studying the delay times between the formation of two bonds. The delay time distribution, used extensively in earlier studies, is placed on a firm dynamical footing by correlating it with the phase space manifolds, determined using the technique of Lagrangian descriptors. We establish the utility of Lagrangian descriptors in identifying the phase space manifolds responsible for the dynamically concerted and dynamically sequential pathways.

physics.chem-ph↗
arXiv2020

Classical and quantum dynamical manifestations of index-2 saddles: concerted versus sequential reaction mechanisms

The presence of higher index saddles on a multidimensional potential energy surface is usually assumed to be of little significance in chemical reaction dynamics. Such a viewpoint requires careful reconsideration, thanks to elegant experiments and novel theoretical approaches that have come about in recent years. In this work, we perform a detailed classical and quantum dynamical study of a model two degree of freedom Hamiltonian, which captures the essence of the debate regarding the dominance of a concerted or a stepwise reaction mechanism. We show that the ultrafast shift of the mechanism from a concerted to a stepwise one is essentially a classical dynamical effect. In addition, due to the classical phase space being a mixture of regular and chaotic dynamics, it is possible to have a rich variety of dynamical behaviour, including a Murrell-Laidler type of mechanism, even at energies sufficiently above that of the index-2 saddle. We rationalize the dynamical results using an explicit construction of the classical invariant manifolds in the phase space.

physics.chem-ph↗
arXiv2020

Intramolecular vibrational energy redistribution and the quantum ergodicity transition: a phase space perspective

Intramolecular vibrational energy redistribution (IVR) impacts the dynamics of reactions in a profound way. Theoretical and experimental studies are increasingly indicating that accounting for the finite rate of energy flow is critical for uncovering the correct reaction mechanisms and calculating accurate rates. This requires an explicit understanding of the influence and interplay of the various anharmonic (Fermi) resonances that lead to the coupling of the vibrational modes. In this regard, the local random matrix theory (LRMT) and the related Bose-statistics triangle rule (BSTR) model have emerged as a powerful and predictive quantum theories for IVR. In this Perspective we highlight the close correspondence between LRMT and the classical phase space perspective on IVR, primarily using model Hamiltonians with three degrees of freedom. Our purpose for this is threefold. First, this clearly brings out the extent to which IVR pathways are essentially classical, and hence crucial towards attempts to control IVR. Second, given that LRMT and BSTR are designed to be applicable for large molecules, the exquisite correspondence observed even for small molecules allows for insights into the quantum ergodicity transition. Third, we showcase the power of modern nonlinear dynamics methods in analysing high dimensional phase spaces, thereby extending the deep insights into IVR that were earlier gained for systems with effectively two degrees of freedom. We begin with a brief overview of recent examples where IVR plays an important role and conclude by mentioning the outstanding problems and the potential connections to issues of interest in other fields.

nlin.CD↗
arXiv2020

Stable chaos and delayed onset of statisticality in unimolecular dissociation reactions

Statistical models provide a powerful and useful class of approximations for calculating reaction rates by bypassing the need for detailed, and often difficult, dynamical considerations. Such approaches invariably invoke specific assumptions about the extent of intramolecular vibrational energy flow in the system. However, the nature of the transition to the statistical regime as a function of the molecular parameters is far from being completely understood. Here, we use tools from nonlinear dynamics to study the transition to statisticality in a model unimolecular reaction by explicitly visulaizing the high dimensional classical phase space. We identify generic features in the phase space involving the intersection of two or more independent anharmonic resonances and show that the presence of correlated, but chaotic, intramolecular dynamics near such junctions leads to nonstatisticality. Interestingly, akin to the stability of asteroids in the Solar System, molecules can stay protected from dissociation at the junctions for several picoseconds due to the phenomenon of stable chaos.

physics.chem-ph↗
arXiv2018

Relevance of the resonance junctions on the Arnold web to dynamical tunneling and eigenstate delocalization

In this work we study the competition and correspondence between the classical and quantum routes to intramolecular vibrational energy redistribution (IVR) in a three degrees of freedom model effective Hamiltonian. Specifically, we focus on the classical and the quantum dynamics near the resonance junctions on the Arnold web that are formed by intersection of independent resonances. The regime of interest models the IVR dynamics from highly excited initial states near dissociation thresholds of molecular systems wherein both classical and purely quantum, involving dynamical tunneling, routes to IVR coexist. In the vicinity of a resonance junction classical chaos is inevitably present and hence one expects the quantum IVR pathways to have a strong classical component as well. We show that with increasing resonant coupling strengths the classical component of IVR leads to a transition from coherent dynamical tunneling to incoherent dynamical tunneling. Furthermore, we establish that the quantum IVR dynamics can be predicted based on the structures on the classical Arnold web. In addition, we investigate the nature of the highly excited eigenstates in order to identify the quantum signatures of the multiplicity-2 junctions. For the parameter regimes studies herein, by projecting the eigenstates onto the Arnold web, we find that eigenstates in the vicinity of the junctions are primarily delocalized due to dynamical tunneling.

nlin.CD↗
arXiv2014

Bichromatic control of dynamical tunneling: influence of the irregular Floquet states

Bichromatic control, in terms of the amplitude and relative phase of the second field as control knobs, is an useful approach for controlling a variety of quantum processes. In this context, understanding the features of the control landscape is important to assess the extent and efficiency of the control process. A key question is whether, for a given quantum process, one can have regions wherein there is a complete lack of control. In this work we show that such regions do exist and can be explained on the basis of the phase space nature of the quantum Floquet states. Specifically, we show that robust regions of no control arise due to the phenomenon of chaos-assisted tunneling. We also comment on the possible influence of such regions on the phenomenon of directed transport in quantum Hamiltonian ratchets.

nlin.CD↗
arXiv2013

Eigenstates of Thiophosgene Near the Dissociation Threshold -- Deviations From Ergodicity

A subset of the highly excited eigenstates of thiophosgene (SCCl$_{2}$) near the dissociation threshold are analyzed using sensitive measures of quantum ergodicity. We find several localized eigenstates, suggesting that the intramolecular vibrational energy flow dynamics is nonstatistical even at such high levels of excitations. The results are consistent with recent observations of sharp spectral features in the stimulated emission spectra of SCCl$_{2}$

physics.chem-ph↗
arXiv2012

Driven coupled Morse oscillators --- visualizing the phase space and characterizing the transport

Recent experimental and theoretical studies indicate that intramolecular energy redistribution (IVR) is nonstatistical on intermediate timescales even in fairly large molecules. Therefore, it is interesting to revisit the the old topic of IVR versus quantum control and one expects that a classical-quantum perspective is appropriate to gain valuable insights into the issue. However, understanding classical phase space transport in driven systems is a prerequisite for such a correspondence based approach and is a challenging task for systems with more then two degrees of freedom. In this work we undertake a detailed study of the classical dynamics of a minimal model system - two kinetically coupled coupled Morse oscillators in the presence of a monochromatic laser field. Using the technique of wavelet transforms a representation of the high dimensional phase space, the resonance network or Arnold web, is constructed and analysed. The key structures in phase space which regulate the dissociation dynamics are identified. Furthermore, we show that the web is nonuniform with the classical dynamics exhibiting extensive stickiness, resulting in anomalous transport. Our work also shows that pairwise irrational barriers might be crucial even in higher dimensional systems.

nlin.CD↗
arXiv2011

On the nature of highly vibrationally excited states of Thiophosgene

In this work an analysis of the highly vibrationally excited states of thiophosgene (SCCl$_{2}$) is made in order to gain insights into some of the experimental observations and spectral features. The states analyzed herein lie in a spectrally complex region where strong mode mixings are expected due to the overlap of several strong anharmonic Fermi resonances. Two recent techniques, a semiclassical angle space representation of the eigenstates and the parametric variation of the eigenvalues (level-velocities) are used to identify eigenstate sequences exhibiting common localization characteristics. Preliminary results on the influence of highly excited out-of-plane bending modes on the nature of the eigenstates suggest a possible bifurcation in the system.

physics.chem-ph↗
arXiv2011

Dynamical tunneling and control

This article summarizes the recent work on the influence of dynamical tunneling on the control of quantum systems. Specifically, two examples are discussed. In the first, it is shown that the bichromatic control of tunneling in a driven double well system is hampered by the phenomenon of chaos-assisted tunneling. The bichromatic control landscape exhibits several regions indicating lack of control with every such region involving chaos-assisted tunneling. The second example illustrates the failure of controlling the dissociation dynamics of a driven Morse oscillator due to the phenomenon of resonance-assisted tunneling. In particular, attempts to control the dissociation dynamics by rebuilding local phase space barriers are foiled due to resonance-assisted tunneling.

nlin.CD↗
arXiv2008

Local phase space control and interplay of classical and quantum effects in dissociation of a driven Morse oscillator

This work explores the possibility of controlling the dissociation of a monochromatically driven one-dimensional Morse oscillator by recreating barriers, in the form of invariant tori with irrational winding ratios, at specific locations in the phase space. The control algorithm proposed by Huang {\it et al.} (Phys. Rev. A {\bf 74}, 053408 (2006)) is used to obtain an analytic expression for the control field. We show that the control term, approximated as an additional weaker field, is efficient in recreating the desired tori and suppresses the classical as well as the quantum dissociation. However, in the case when the field frequency is tuned close to a two-photon resonance the local barriers are not effective in suppressing the dissociation. We establish that in the on-resonant case quantum dissociation primarily occurs via resonance-assisted tunneling and controlling the quantum dynamics requires a local perturbation of the specific nonlinear resonance in the underlying phase space.

nlin.CD↗
arXiv2008

Bichromatically driven double well: parametric perspective of the strong-field control landscape reveals the influence of chaotic states

The aim of this work is to understand the influence of chaotic states in control problems involving strong fields. Towards this end, we numerically construct and study the strong field control landscape of a bichromatically driven double well. A novel measure based on correlating the overlap intensities between Floquet states and an initial phase space coherent state with the parametric motion of the quasienergies is used to construct and interpret the landscape features. "Walls" of no control, robust under variations of the relative phase between the fields, are seen on the control landscape and associated with multilevel interactions involving chaotic Floquet states.

nlin.CD↗
arXiv2007

Dynamical tunneling in molecules: Quantum routes to energy flow

Dynamical tunneling, introduced in the molecular context, is more than two decades old and refers to phenomena that are classically forbidden but allowed by quantum mechanics. On the other hand the phenomenon of intramolecular vibrational energy redistribution (IVR) has occupied a central place in the field of chemical physics for a much longer period of time. Although the two phenomena seem to be unrelated several studies indicate that dynamical tunneling, in terms of its mechanism and timescales, can have important implications for IVR. Examples include the observation of local mode doublets, clustering of rotational energy levels, and extremely narrow vibrational features in high resolution molecular spectra. Both the phenomena are strongly influenced by the nature of the underlying classical phase space. This work reviews the current state of understanding of dynamical tunneling from the phase space perspective and the consequences for intramolecular vibrational energy flow in polyatomic molecules.

physics.chem-ph↗
arXiv2007

Bichromatically driven double well: Parametric perspective of the control landscape

We numerically construct and study the control landscape of a $(ω,2ω)$ bichromatically driven double well in the presence of strong fields. The control landscape is obtained by correlating the overlap intensities between the floquet states and an initial phase space coherent state with the parametric motion of the quasienergies {\it i.e.,} intensity-level velocity correlator. "Walls" of no control, robust under variations of the relative phase between the fields, are seen in the control landscape and associated with multilevel interactions involving chaotic floquet states.

nlin.CD↗