The role of quantum intramolecular dynamics in unimolecular reactions

1990 ◽  
Vol 332 (1625) ◽  
pp. 203-220 ◽  
Keyword(s):  
Equations Of Motion ◽  
Classical Mechanics ◽  
Spin Symmetry ◽  
Zero Point ◽  
Fermi Resonance ◽  
Intramolecular Dynamics ◽  
Coupled Modes ◽  
Potential Surfaces ◽  
Unimolecular Reactions ◽  
Point Energy

The dynamics of unimolecular reactions can be modelled by classical mechanics for the motion of nuclei on Born-Oppenheimer or other effective potential surfaces, by the corresponding quantum mechanical equations of motion and, perhaps, by quantum statistical treatments. In this paper I provide a synopsis of fundamental, qualitatively important effects arising from the quantum nature of intramolecular dynamics, as opposed to classical mechanics, and illustrate these with theoretical predictions and experimental examples from the work of my group in Zurich. These include quantum nonlinearity in infrared (IR) multiphoton excitation and reaction, non-classical wavepacket spreading in the Fermi resonance coupled modes in CHX3 molecules, effects of zero point energy and angular momentum in unimolecular reactions, nuclear spin symmetry conservation and inter con version and the hypothetical effects arising from the violation of parity and time reversal symmetry in unimolecular reactions. Specific applications to experiments include IR laser chemistry of CF3I and CF3Br, IR spectroscopy and dynamics of CHF3 and predissociation spectra and dynamics of II

Relationship Between the Zero Point Energy of a Polyatomic Molecule and its Molecular Structure

1973 ◽  
Vol 28 (2) ◽  
pp. 123-128 ◽  
Author(s):  
Jacob Bigeleisen ◽  
M. W. Lee
Keyword(s):  
Equations Of Motion ◽  
Zero Point ◽  
Convergent Series ◽  
Harmonic Oscillators ◽  
Zero Point Energy ◽  
Point Energy ◽  
The Matrix ◽  
Definition Of ◽  
The Individual ◽  
Detailed Application

Criteria are established for the definition of the mean characteristic eigenvalue, λ0, of a system of coupled harmonic oscillators. The first criterion is that λ0 lead to a convergent series for the zero point energy of the systems; the second criterion is that λ0 be obtained directly from the matrix elements of the equations of motion, without solution for the individual eigenvalues. Two general types of λ0's are found and their properties are discussed. Detailed application is made to the zero point energy differences of the isotopic methanes, ethylenes and benzenes.

On the Use of Quantum Thermal Bath in Unimolecular Fragmentation Simulations

2019 ◽  
Author(s):  
Riccardo Spezia ◽  
Hichem Dammak
Keyword(s):  
Degrees Of Freedom ◽  
Molecular Simulations ◽  
Zero Point ◽  
Thermal Bath ◽  
Unimolecular Dissociation ◽  
Point Energy ◽  
Rotational Degrees Of Freedom ◽  
The Difference ◽  
Nuclear Effects

<div> <div> <div> <p>In the present work we have investigated the possibility of using the Quantum Thermal Bath (QTB) method in molecular simulations of unimolecular dissociation processes. Notably, QTB is aimed in introducing quantum nuclear effects with a com- putational time which is basically the same as in newtonian simulations. At this end we have considered the model fragmentation of CH4 for which an analytical function is present in the literature. Moreover, based on the same model a microcanonical algorithm which monitor zero-point energy of products, and eventually modifies tra- jectories, was recently proposed. We have thus compared classical and quantum rate constant with these different models. QTB seems to correctly reproduce some quantum features, in particular the difference between classical and quantum activation energies, making it a promising method to study unimolecular fragmentation of much complex systems with molecular simulations. The role of QTB thermostat on rotational degrees of freedom is also analyzed and discussed. </p> </div> </div> </div>

scholarly journals Modulation of optical absorption in m-Fe1−xRuxS2 and exploring stability in new m-RuS2

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
H. Joshi ◽  
M. Ram ◽  
N. Limbu ◽  
D. P. Rai ◽  
B. Thapa ◽  
...  
Keyword(s):  
Optical Absorption ◽  
Phonon Dispersion ◽  
Applied Pressure ◽  
Orthorhombic Phase ◽  
Zero Point ◽  
Computational Method ◽  
Crystal Field Theory ◽  
Point Energy ◽  
Practical Applications ◽  
New Phase

AbstractA first-principle computational method has been used to investigate the effects of Ru dopants on the electronic and optical absorption properties of marcasite FeS2. In addition, we have also revealed a new marcasite phase in RuS2, unlike most studied pyrite structures. The new phase has fulfilled all the necessary criteria of structural stability and its practical existence. The transition pressure of 8 GPa drives the structural change from pyrite to orthorhombic phase in RuS2. From the thermodynamical calculation, we have reported the stability of new-phase under various ranges of applied pressure and temperature. Further, from the results of phonon dispersion calculated at Zero Point Energy, pyrite structure exhibits ground state stability and the marcasite phase has all modes of frequencies positive. The newly proposed phase is a semiconductor with a band gap comparable to its pyrite counterpart but vary in optical absorption by around 106 cm−1. The various Ru doped structures have also shown similar optical absorption spectra in the same order of magnitude. We have used crystal field theory to explain high optical absorption which is due to the involvement of different electronic states in formation of electronic and optical band gaps. Lӧwdin charge analysis is used over the customarily Mulliken charges to predict 89% of covalence in the compound. Our results indicate the importance of new phase to enhance the efficiency of photovoltaic materials for practical applications.

scholarly journals A least action principle for interceptive walking

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Soon Ho Kim ◽  
Jong Won Kim ◽  
Hyun Chae Chung ◽  
MooYoung Choi
Keyword(s):  
Social Systems ◽  
Equations Of Motion ◽  
Classical Mechanics ◽  
Action Principle ◽  
Lagrange Equations ◽  
Least Action Principle ◽  
Least Action ◽  
The Least Action Principle ◽  
Principle Of Least Action ◽  
Human Participants

AbstractThe principle of least effort has been widely used to explain phenomena related to human behavior ranging from topics in language to those in social systems. It has precedence in the principle of least action from the Lagrangian formulation of classical mechanics. In this study, we present a model for interceptive human walking based on the least action principle. Taking inspiration from Lagrangian mechanics, a Lagrangian is defined as effort minus security, with two different specific mathematical forms. The resulting Euler–Lagrange equations are then solved to obtain the equations of motion. The model is validated using experimental data from a virtual reality crossing simulation with human participants. We thus conclude that the least action principle provides a useful tool in the study of interceptive walking.

scholarly journals Dynamical strengthening of covalent and non-covalent molecular interactions by nuclear quantum effects at finite temperature

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Huziel E. Sauceda ◽  
Valentin Vassilev-Galindo ◽  
Stefan Chmiela ◽  
Klaus-Robert Müller ◽  
Alexandre Tkatchenko
Keyword(s):  
Finite Temperature ◽  
Electrostatic Interactions ◽  
Zero Point ◽  
Quantum Effects ◽  
Van Der Waals Interactions ◽  
Interatomic Distances ◽  
Point Energy ◽  
Molecular Bond ◽  
Energy Surfaces ◽  
Nuclear Quantum Effects

AbstractNuclear quantum effects (NQE) tend to generate delocalized molecular dynamics due to the inclusion of the zero point energy and its coupling with the anharmonicities in interatomic interactions. Here, we present evidence that NQE often enhance electronic interactions and, in turn, can result in dynamical molecular stabilization at finite temperature. The underlying physical mechanism promoted by NQE depends on the particular interaction under consideration. First, the effective reduction of interatomic distances between functional groups within a molecule can enhance the n → π* interaction by increasing the overlap between molecular orbitals or by strengthening electrostatic interactions between neighboring charge densities. Second, NQE can localize methyl rotors by temporarily changing molecular bond orders and leading to the emergence of localized transient rotor states. Third, for noncovalent van der Waals interactions the strengthening comes from the increase of the polarizability given the expanded average interatomic distances induced by NQE. The implications of these boosted interactions include counterintuitive hydroxyl–hydroxyl bonding, hindered methyl rotor dynamics, and molecular stiffening which generates smoother free-energy surfaces. Our findings yield new insights into the versatile role of nuclear quantum fluctuations in molecules and materials.

scholarly journals Time-Resolved Measurements and Master Equation Modelling of the Unimolecular Decomposition of CH3OCH2

2020 ◽  
Vol 234 (7-9) ◽  
pp. 1233-1250 ◽  
Author(s):  
Arrke J. Eskola ◽  
Mark A. Blitz ◽  
Michael J. Pilling ◽  
Paul W. Seakins ◽  
Robin J. Shannon
Keyword(s):  
Energy Transfer ◽  
Master Equation ◽  
Rate Coefficient ◽  
Zero Point ◽  
Buffer Gas ◽  
Unimolecular Decomposition ◽  
Time Resolved ◽  
Point Energy ◽  
Wide Range ◽  
Transfer Parameters

AbstractThe rate coefficient for the unimolecular decomposition of CH3OCH2, k1, has been measured in time-resolved experiments by monitoring the HCHO product. CH3OCH2 was rapidly and cleanly generated by 248 nm excimer photolysis of oxalyl chloride, (ClCO)2, in an excess of CH3OCH3, and an excimer pumped dye laser tuned to 353.16 nm was used to probe HCHO via laser induced fluorescence. k1(T,p) was measured over the ranges: 573–673 K and 0.1–4.3 × 1018 molecule cm−3 with a helium bath gas. In addition, some experiments were carried out with nitrogen as the bath gas. Ab initio calculations on CH3OCH2 decomposition were carried out and a transition-state for decomposition to CH3 and H2CO was identified. This information was used in a master equation rate calculation, using the MESMER code, where the zero-point-energy corrected barrier to reaction, ΔE0,1, and the energy transfer parameters, ⟨ΔEdown⟩ × Tn, were the adjusted parameters to best fit the experimental data, with helium as the buffer gas. The data were combined with earlier measurements by Loucks and Laidler (Can J. Chem.1967, 45, 2767), with dimethyl ether as the third body, reinterpreted using current literature for the rate coefficient for recombination of CH3OCH2. This analysis returned ΔE0,1 = (112.3 ± 0.6) kJ mol−1, and leads to $k_{1}^{\infty}(T)=2.9\times{10^{12}}$ (T/300)2.5 exp(−106.8 kJ mol−1/RT). Using this model, limited experiments with nitrogen as the bath gas allowed N2 energy transfer parameters to be identified and then further MESMER simulations were carried out, where N2 was the buffer gas, to generate k1(T,p) over a wide range of conditions: 300–1000 K and N2 = 1012–1025 molecule cm−3. The resulting k1(T,p) has been parameterized using a Troe-expression, so that they can be readily be incorporated into combustion models. In addition, k1(T,p) has been parametrized using PLOG for the buffer gases, He, CH3OCH3 and N2.

VACUUM ENERGY IN SPHERICAL DOMAINS: WKB AND UNIFORM ASYMPTOTIC EXPANSIONS

1996 ◽  
Vol 11 (22) ◽  
pp. 4129-4146 ◽  
Author(s):  
AUGUST ROMEO
Keyword(s):  
Zeta Function ◽  
Asymptotic Expansions ◽  
Zero Point ◽  
Massless Scalar ◽  
Massless Scalar Field ◽  
Point Energy ◽  
Dimensional Dependence ◽  
Spherical Domains ◽  
Spectral Zeta Function ◽  
Uniform Asymptotic Expansions

We evaluate the finite part of the regularized zero-point energy for a massless scalar field confined in the interior of a D-dimensional spherical region. While some insight is offered into the dimensional dependence of the WKB approximations by examining the residues of the spectral-zeta-function poles, a mode-sum technique based on an integral representation of the Bessel spectral zeta function is applied with the help of uniform asymptotic expansions (u.a.e.’s).

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