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 Chemical Physics (24)
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 Ground states (3)
 Quantum optics (3)
 Semiclassical methods (2)
 Non adiabatic reactions (2)
 Physical Chemistry, Chemical Physics (2)
 Hydrogen reactions (2)
 Hydrogen bonding (2)
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 Chemical Physics, Physical Chemistry (2)
 Ab initio calculations (2)
 Ab initio (2)
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 Biology, Chemistry, Physics (2)
 Lagrangian mechanics (2)
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 Axial elongation (1)
 3nitroformazan (1)
 2D crystallization (1)
 Acids (1)
 Angular momentum (1)
Articles 1  30 of 34
FullText Articles in Physics
Enhanced Nucleate Boiling On Horizontal HydrophobicHydrophilic Carbon Nanotube Coatings, Xianming Dai, Xinyu Huang, Fanghao Yang, Xiaodong Li, Joshua Sightler, Yingchao Yang, Chen Li
Enhanced Nucleate Boiling On Horizontal HydrophobicHydrophilic Carbon Nanotube Coatings, Xianming Dai, Xinyu Huang, Fanghao Yang, Xiaodong Li, Joshua Sightler, Yingchao Yang, Chen Li
Faculty Publications
Ideal hydrophobichydrophilic composite cavities are highly desired to enhance nucleate boiling. However, it is challenging and costly to fabricate these types of cavities by conventional micro/nano fabrication techniques. In this study, a type of hydrophobichydrophilic composite interfaces were synthesized from functionalized multiwall carbon nanotubes by introducing hydrophilic functional groups on the pristine multiwall carbon nanotubes. This type of carbon nanotube enabled hydrophobichydrophilic composite interfaces were systematically characterized. Ideal cavities created by the interfaces were experimentally demonstrated to be the primary reason to substantially enhance nucleate boiling
The Schrödinger Equation With Friction From The Quantum Trajectory Perspective, Sophya V. Garashchuk, V. Dixit, B. Gu, J. Mazzuca
The Schrödinger Equation With Friction From The Quantum Trajectory Perspective, Sophya V. Garashchuk, V. Dixit, B. Gu, J. Mazzuca
Faculty Publications
Similarity of equations of motion for the classical and quantum trajectories is used to introduce afriction term dependent on the wavefunction phase into the timedependent Schrödingerequation. The term describes irreversible energy loss by the quantum system. The force offriction is proportional to the velocity of a quantum trajectory. The resulting Schrödinger equationis nonlinear, conserves wavefunction normalization, and evolves an arbitrary wavefunction into the ground state of the system (of appropriate symmetry if applicable). Decrease in energy is proportional to the average kinetic energy of the quantum trajectory ensemble. Dynamics in the high friction regime is suitable for simple models of ...
Incorporation Of Quantum Effects For Selected Degrees Of Freedom Into The TrajectoryBased Dynamics Using Spatial Domains, Sophya V. Garashchuk, M. V. Volkov
Incorporation Of Quantum Effects For Selected Degrees Of Freedom Into The TrajectoryBased Dynamics Using Spatial Domains, Sophya V. Garashchuk, M. V. Volkov
Faculty Publications
The approach of defining quantum corrections on nuclear dynamics of molecular systems incorporated approximately into selected degrees of freedom, is described. The approach is based on the MadelungdeBroglieBohm formulation of timedependent quantum mechanics which represents a wavefunction in terms of an ensemble of trajectories. The trajectories follow classical laws of motion except that the quantum potential, dependent on the wavefunction amplitude and its derivatives, is added to the external, classical potential. In this framework the quantum potential, determined approximately for practical reasons, is included only into the “quantum” degrees of freedom describing light particles such as protons, while neglecting with ...
Systematic Approach To Electrostatically Induced 2d Crystallization Of Nanoparticles At Liquid Interfaces, S. Kewalramani, S. Wang, Y. Lin, H. G. Nguyen, Qian Wang, M. Fukuto, L. Yang
Systematic Approach To Electrostatically Induced 2d Crystallization Of Nanoparticles At Liquid Interfaces, S. Kewalramani, S. Wang, Y. Lin, H. G. Nguyen, Qian Wang, M. Fukuto, L. Yang
Faculty Publications
We report an experimental demonstration of a strategy for inducing twodimensional (2D)crystallization of charged nanoparticles on oppositely charged fluid interfaces. This strategy aims to maximize the interfacial adsorption of nanoparticles, and hence their lateral packing density, by utilizing a combination of weakly charged particles and a high surface charge density on the planar interface. In order to test this approach, we investigated the assembly of cowpea mosaic virus (CPMV) on positively charged lipid monolayers at the aqueous solution surface, by means of in situXray scattering measurements at the liquid–vapor interface. Theassembly was studied as a function of ...
Efficient Quantum Trajectory Representation Of Wavefunctions Evolving In Imaginary Time, Sophya V. Garashchuk, J. Mazzuca, T. Vazhappilly
Efficient Quantum Trajectory Representation Of Wavefunctions Evolving In Imaginary Time, Sophya V. Garashchuk, J. Mazzuca, T. Vazhappilly
Faculty Publications
The Boltzmann evolution of a wavefunction can be recast as imaginarytime dynamics of the quantum trajectory ensemble. The quantum effects arise from the momentumdependent quantum potential – computed approximately to be practical in highdimensional systems – influencing the trajectories in addition to the external classical potential [S. Garashchuk, J. Chem. Phys.132, 014112 (2010)]. For a nodelesswavefunction represented as ψ(x, t) = exp ( −S(x, t)/ℏ) with the trajectory momenta defined by ∇S(x, t), analysis of the Lagrangian and Eulerian evolution shows that for bound potentials the former is more accurate while the latter is more practical because the Lagrangian ...
Dynamic Path Bifurcation For The Beckmann Reaction: Observation And Implication, H. Yamataka, M. Sato, H. Hasegawa, Salai Cheettu Ammal
Dynamic Path Bifurcation For The Beckmann Reaction: Observation And Implication, H. Yamataka, M. Sato, H. Hasegawa, Salai Cheettu Ammal
Faculty Publications
The reaction of oximes to amides, known as the Beckmann rearrangement, may undergo fragmentation to form carbocations + nitriles instead of amides when the cations have reasonable stability. The reactions of oxime derivatives of 1substitutedphenyl2propanones and 3substitutedphenyl2butanones in aqueous solvents gave both rearrangement and fragmentation products, the ratio of which was dependent on substituents. Transition state (TS) optimizations and intrinsic reaction coordinate (IRC) calculations for the reaction of 1phenyl2propanone oximes showed that there is a single TS for each substituted compound. The IRC path from the TS either led to a rearrangement product or a fragmentation product depending on the substituent ...
Modeling The Noble Metal/Tio_{2} (110) Interface With Hybrid Dft Functionals: A Periodic Electrostatic Embedded Cluster Model Study, Salai Cheettu Ammal, Andreas Heyden
Modeling The Noble Metal/Tio2 (110) Interface With Hybrid Dft Functionals: A Periodic Electrostatic Embedded Cluster Model Study, Salai Cheettu Ammal, Andreas Heyden
Faculty Publications
The interaction of Aun and Ptn (n=2,3) clusters with the stoichiometric and partially reduced rutile TiO2 (110) surfaces has been investigated using periodic slab and periodic electrostatic embedded cluster models. Compared to Au clusters, Pt clusters interact strongly with both stoichiometric and reduced TiO2 (110) surfaces and are able to enhance the reducibility of the TiO2 (110) surface, i.e., reduce the oxygen vacancy formation energy. The focus of this study is the effect of Hartree–Fock exchange on the description of the strength of chemical bonds at the interface of Au/Pt clusters and the TiO2 (110 ...
A Dielectric Affinity Microbiosensor, X. Huang, S. Li, J. S. Schultz, Qian Wang, Q. Lin
A Dielectric Affinity Microbiosensor, X. Huang, S. Li, J. S. Schultz, Qian Wang, Q. Lin
Faculty Publications
We present an affinity biosensing approach that exploits changes in dielectric properties of a polymer due to its specific, reversible binding with an analyte. The approach is demonstrated using a microsensor comprising a pair of thinfilm capacitive electrodes sandwiching a solution of poly(acrylamideran3acrylamidophenylboronic acid), a synthetic polymer with specific affinity to glucose. Binding with glucose induces changes in the permittivity of the polymer, which can be measured capacitively for specific glucose detection, as confirmed by experimental results at physiologically relevant concentrations. The dielectric affinity biosensing approach holds the potential for practical applications such as longterm continuous glucose ...
Quantum Trajectory Dynamics In Imaginary Time With The MomentumDependent Quantum Potential, Sophya V. Garashchuk
Quantum Trajectory Dynamics In Imaginary Time With The MomentumDependent Quantum Potential, Sophya V. Garashchuk
Faculty Publications
The quantum trajectory dynamics is extended to the wave function evolution in imaginary time. For a nodelesswave function a simple exponential form leads to the classicallike equations of motion of trajectories, representing the wave function, in the presence of the momentumdependent quantum potential in addition to the external potential. For a Gaussian wave function this quantum potential is a timedependent constant, generating zero quantum force yet contributing to the total energy. For anharmonic potentials the momentumdependent quantum potential is cheaply estimated from the global Leastsquares Fit to the trajectory momenta in the Taylor basis. Wave functions with nodes are described ...
Wavepacket Approach To The Cumulative Reaction Probability Within The Flux Operator Formalism, Sophya V. Garashchuk, T. Vazhappilly
Wavepacket Approach To The Cumulative Reaction Probability Within The Flux Operator Formalism, Sophya V. Garashchuk, T. Vazhappilly
Faculty Publications
Expressions for the singular flux operator eigenfunctions and eigenvalues are given in terms of the Diracδfunction representable as a localized Gaussian wavepacket. This functional form enables computation of the cumulative reaction probability N(E) from the wavepacket timecorrelation functions. The Gaussian based form of the flux eigenfunctions, which is not tied to a finite basis of a quantummechanical calculation, is particularly useful for approximate calculation of N(E) with the trajectory based wavepacket propagation techniques. Numerical illustration is given for the Eckart barrier using the conventional quantummechanical propagation and the quantum trajectory dynamics with the approximate quantum potential. N(E ...
Stable LongTime Semiclassical Description Of ZeroPoint Energy In HighDimensional Molecular Systems, Sophya V. Garashchuk, V. A. Rassolov
Stable LongTime Semiclassical Description Of ZeroPoint Energy In HighDimensional Molecular Systems, Sophya V. Garashchuk, V. A. Rassolov
Faculty Publications
Semiclassical implementation of the quantum trajectory formalism [J. Chem. Phys.120, 1181 (2004)] is further developed to give a stable longtime description of zeropoint energy in anharmonic systems of high dimensionality. The method is based on a numerically cheap linearized quantum force approach; stabilizing terms compensating for the linearization errors are added into the timeevolution equations for the classical and nonclassical components of the momentum operator. The wave function normalization and energy are rigorously conserved. Numerical tests are performed for model systems of up to 40 degrees of freedom.
Computation Of Correlation Functions And Wave Function Projections In The Context Of Quantum Trajectory Dynamics, Sophya V. Garashchuk
Computation Of Correlation Functions And Wave Function Projections In The Context Of Quantum Trajectory Dynamics, Sophya V. Garashchuk
Faculty Publications
The de BroglieBohm formulation of the Schrödinger equation implies conservation of the wave functionprobability density associated with each quantum trajectory in closed systems. This conservation property greatly simplifies numerical implementations of the quantum trajectory dynamics and increases its accuracy. The reconstruction of a wave function, however, becomes expensive or inaccurate as it requires fitting or interpolation procedures. In this paper we present a method of computing wave packet correlation functions and wave function projections, which typically contain all the desired information about dynamics, without the full knowledge of the wave function by making quadratic expansions of the wave function phase ...
Semiclassical Nonadiabatic Dynamics Based On Quantum Trajectories For The O(^{3}P,^{1}D) + H_{2} System, Sophya V. Garashchuk, V. A. Rassolov, G. C. Schatz
Semiclassical Nonadiabatic Dynamics Based On Quantum Trajectories For The O(3P,1D) + H2 System, Sophya V. Garashchuk, V. A. Rassolov, G. C. Schatz
Faculty Publications
The O(P3,D1)+H2→OH+Hreaction is studied using trajectory dynamics within the approximate quantum potential approach. Calculations of the wavepacket reaction probabilities are performed for four coupled electronic states for total angular momentum J=0 using a mixed coordinate/polar representation of the wave function. Semiclassical dynamics is based on a single set of trajectories evolving on an effective potentialenergy surface and in the presence of the approximate quantum potential. Population functions associated with each trajectory are computed for each electronic state. The effective surface is a linear combination of the electronic states with the contributions of individual ...
Semiclassical Nonadiabatic Dynamics Using A Mixed WaveFunction Representation, Sophya V. Garashchuk, V. A. Rassolov, G. C. Schatz
Semiclassical Nonadiabatic Dynamics Using A Mixed WaveFunction Representation, Sophya V. Garashchuk, V. A. Rassolov, G. C. Schatz
Faculty Publications
Nonadiabaticeffects in quantum dynamics are described using a mixed polar/coordinate space representation of the wave function. The polar part evolves on dynamically determined potential surfaces that have diabatic and adiabatic potentials as limiting cases of weak localized and strong extended diabatic couplings. The coordinate space part, generalized to a matrix form, describes transitions between the surfaces. Choice of the effective potentials for the polar part and partitioning of the wave function enables one to represent the total wave function in terms of smooth components that can be accurately propagated semiclassically using the approximate quantum potential and small basis sets ...
Semiclassical Nonadiabatic Dynamics With Quantum Trajectories, Vitaly A. Rassolov, Sophya V. Garashchuk
Semiclassical Nonadiabatic Dynamics With Quantum Trajectories, Vitaly A. Rassolov, Sophya V. Garashchuk
Faculty Publications
Dynamics based on quantum trajectories with approximate quantum potential is generalized to nonadiabatic systems and its semiclassical properties are discussed. The formulation uses the mixed polarcoordinate space representation of a wave function. The polar part describes the overall time evolution of the wavefunction components semiclassically using the singlesurface approximate quantum potential. The coordinate part represents a complex“population” amplitude, which in case of localized coupling can be solved for quantum mechanically in an efficient manner. In the highenergy regime this is accomplished by using a small basis determined by the coupling between surfaces. An illustration is given for a typical ...
Growth And Transport Properties Of Complementary Germanium Nanowire Field Effect Transistors, Andrew B. Greytak, Lincoln J. Lauhon, Mark S. Gudiksen, Charles M. Lieber
Growth And Transport Properties Of Complementary Germanium Nanowire Field Effect Transistors, Andrew B. Greytak, Lincoln J. Lauhon, Mark S. Gudiksen, Charles M. Lieber
Faculty Publications
n and ptype Ge nanowires were synthesized by a multistep process in which axial elongation, via vapor–liquid–solid (VLS) growth, and doping were accomplished in separate chemical vapor deposition steps. Intrinsic, singlecrystal, Ge nanowires prepared by Au nanoclustermediated VLS growth were surfacedoped in situ using diborane or phosphine, and then radial growth of an epitaxial Ge shell was used to cap the dopant layer. Fieldeffect transistors prepared from these Ge nanowires exhibited on currents and transconductances up to 850 µA/µm and 4.9 µA/V, respectively, with device yields of >85%.
Energy Conserving Approximations To The Quantum Potential: Dynamics With Linearized Quantum Force, Sophya V. Garashchuk, V. A. Rassolov
Energy Conserving Approximations To The Quantum Potential: Dynamics With Linearized Quantum Force, Sophya V. Garashchuk, V. A. Rassolov
Faculty Publications
Solution of the Schrödinger equation within the de Broglie–Bohm formulation is based on propagation of trajectories in the presence of a nonlocal quantum potential. We present a new strategy for defining approximate quantum potentials within a restricted trial function by performing the optimal fit to the logderivatives of the wave function density. This procedure results in the energyconserving dynamics for a closed system. For one particular form of the trial function leading to the linear quantum force, the optimization problem is solved analytically in terms of the first and second moments of the weighted trajectory distribution. This approach gives ...
Modified Quantum Trajectory Dynamics Using A Mixed Wave Function Representation, Sophya V. Garashchuk, V. A. Rassolov
Modified Quantum Trajectory Dynamics Using A Mixed Wave Function Representation, Sophya V. Garashchuk, V. A. Rassolov
Faculty Publications
Dynamics of quantum trajectories provides an efficient framework for description of various quantum effects in large systems, but it is unstable near the wave function density nodes where the quantum potential becomes singular. A mixed coordinate space/polar representation of the wave function is used to circumvent this problem. The resulting modified trajectory dynamics associated with the polar representation is nonsingular and smooth. The interference structure and the nodes of the wave function density are described, in principle, exactly in the coordinate representation. The approximate version of this approach is consistent with the semiclassical linearized quantum force method [S. Garashchuk ...
Bohmian Dynamics On Subspaces Using Linearized Quantum Force, V. A. Rassolov, Sophya V. Garashchuk
Bohmian Dynamics On Subspaces Using Linearized Quantum Force, V. A. Rassolov, Sophya V. Garashchuk
Faculty Publications
In the de Broglie–Bohm formulation of quantum mechanics the timedependent Schrödinger equation is solved in terms of quantum trajectories evolving under the influence of quantum and classical potentials. For a practical implementation that scales favorably with system size and is accurate for semiclassical systems, we use approximate quantum potentials. Recently, we have shown that optimization of the nonclassical component of the momentum operator in terms of fitting functions leads to the energyconserving approximate quantum potential. In particular, linear fitting functions give the exact time evolution of a Gaussian wave packet in a locally quadratic potential and can describe the ...
Geminal Model Chemistry Ii. Perturbative Corrections, V. A. Rassolov, F. Xu, Sophya V. Garashchuk
Geminal Model Chemistry Ii. Perturbative Corrections, V. A. Rassolov, F. Xu, Sophya V. Garashchuk
Faculty Publications
We introduce and investigate a chemical model based on perturbative corrections to the product of singlettype strongly orthogonal geminals wave function. Two specific points are addressed (i) Overall chemical accuracy of such a model with perturbative corrections at a leading order; (ii) Quality of strong orthogonality approximation of geminals in diverse chemical systems. We use the Epstein–Nesbet form of perturbation theory and show that its known shortcomings disappear when it is used with the reference Hamiltonian based on strongly orthogonal geminals. Application of this model to various chemical systems reveals that strongly orthogonal geminals are well suited for chemical ...
Semiclassical Dynamics With Quantum Trajectories: Formulation And Comparison With The Semiclassical Initial Value Representation Propagator, Sophya V. Garashchuk, V. A. Rassolov
Semiclassical Dynamics With Quantum Trajectories: Formulation And Comparison With The Semiclassical Initial Value Representation Propagator, Sophya V. Garashchuk, V. A. Rassolov
Faculty Publications
We present a timedependent semiclassical method based on quantum trajectories. Quantummechanical effects are described via the quantum potential computed from the wave function density approximated as a linear combination of Gaussian fitting functions. The number of the fitting functions determines the accuracy of the approximate quantum potential (AQP). One Gaussian fit reproduces timeevolution of a Gaussian wave packet in a parabolic potential. The limit of the large number of fitting Gaussians and trajectories gives the full quantummechanical result. The method is systematically improvable from classical to fully quantum. The fitting procedure is implemented as a gradient minimization. We also compare ...
Shape Imprinting Due To Variable Disulfide Bonds In Polyacrylamide Gels, Andrew B. Greytak, Alexander Y. Grosberg, Toyoichi Tanaka
Shape Imprinting Due To Variable Disulfide Bonds In Polyacrylamide Gels, Andrew B. Greytak, Alexander Y. Grosberg, Toyoichi Tanaka
Faculty Publications
Through the use of variable disulfide crosslinkers, we have created polyacrylamide gels whose shape can be altered after polymerization. N,N'bisacryloylcystamine is incorporated as a crosslinker, along with a smaller amount of a permanent crosslinker. After polymerization, the disulfide bonds are cleaved into thiols through reduction. By reoxidizing the thiols with the gel held in a new macroscopic shape, a new set of disulfide bonds is formed, and the gel is forced to adopt the new shape. Retension of the new shape improves with greater distortion from the original shape, as well as with increased concentration of variable disulfide ...
Semiclassical Application Of The Mo/Ller Operators In Reactive Scattering, Sophya V. Garashchuk, J. C. Light
Semiclassical Application Of The Mo/Ller Operators In Reactive Scattering, Sophya V. Garashchuk, J. C. Light
Faculty Publications
Mo/ller operators in the formulation of reaction probabilities in terms of wave packet correlation functions allow us to define the wave packets in the interaction region rather than in the asymptotic region of the potential surface. We combine Mo/ller operators with the semiclassical propagator of Herman and Kluk. This does not involve further approximations and can be used with any initial value representation (IVR) semiclassical propagator. Time propagation in asymptotic regions of the potential due to Mo/ller operators reduces the oscillations of the propagator integrand and improves convergence of the results with respect to the number of ...
Quasirandom Distributed Gaussian Bases For Bound Problems, Sophya V. Garashchuk, J. C. Light
Quasirandom Distributed Gaussian Bases For Bound Problems, Sophya V. Garashchuk, J. C. Light
Faculty Publications
We introduce quasirandom distributed Gaussian bases (QDGB) that are well suited for bound problems. The positions of the basis functions are chosen quasirandomly while their widths and density are functions of the potential. The basis function overlap and kinetic energy matrix elements are analytical. The potential energy matrix elements are accurately evaluated using fewpoint quadratures, since the Gaussian basis functions are localized. The resulting QDGB can be easily constructed and is shown to be accurate and efficient for eigenvalue calculation for several multidimensional model vibrational problems. As more demanding examples, we used a 2D QDGBDVR basis to calculate the lowest ...
Simplified Calculation Of The Stability Matrix For Semiclassical Propagation, Sophya V. Garashchuk, J. C. Light
Simplified Calculation Of The Stability Matrix For Semiclassical Propagation, Sophya V. Garashchuk, J. C. Light
Faculty Publications
We present a simple method of calculation of the stability (monodromy) matrix that enters the widely used semiclassical propagator of Herman and Kluk and almost all other semiclassical propagators. The method is based on the unitarity of classical propagation and does not involve any approximations. The number of auxiliary differential equations per trajectory scales linearly rather than quadratically with the system size. Just the first derivatives of the potential surface are needed. The method is illustrated on the collinear H3 system.
Cumulative Reaction Probability In Terms Of ReactantProduct Wave Packet Correlation Functions, Sophya V. Garashchuk, D. J. Tannor
Cumulative Reaction Probability In Terms Of ReactantProduct Wave Packet Correlation Functions, Sophya V. Garashchuk, D. J. Tannor
Faculty Publications
We present new expressions for the cumulative reaction probability (N(E)), cast in terms of timecorrelation functions of reactant and product wave packets. The derivation begins with a standard trace expression for the cumulative reaction probability, expressed in terms of the reactive scattering matrix elements in an asymptotic internal basis. By combining the property of invariance of the trace with a wave packet correlation function formulation of reactive scattering, we obtain an expression for N(E) in terms of the correlation matrices of incoming and outgoing wave packets which are arbitrary in the internal coordinates. This formulation, like other recent ...
Semiclassical Calculation Of Cumulative Reaction Probabilities, Sophya V. Garashchuk, D. J. Tannor
Semiclassical Calculation Of Cumulative Reaction Probabilities, Sophya V. Garashchuk, D. J. Tannor
Faculty Publications
Calculation of chemical reaction rates lies at the very core of theoretical chemistry. The essential dynamical quantity which determines the reaction rate is the energydependent cumulative reaction probability, N(E), whose Boltzmann average gives the thermal rate constant, k(T). Converged quantum mechanical calculations of N(E) remain a challenge even for three and fouratom systems, and a longstanding goal of theoreticians has been to calculate N(E) accurately and efficiently using semiclassical methods. In this article we present a variety of methods for achieving this goal, by combining semiclassical initial value propagation methods with a reactant–product wavepacket correlation ...
Chemical Signals From Submarine Fluid Advection Onto The Continental Shelf, W. S. Moore, Timothy J. Shaw
Chemical Signals From Submarine Fluid Advection Onto The Continental Shelf, W. S. Moore, Timothy J. Shaw
Faculty Publications
No abstract provided.
Ab Initio And Dft Investigations Of Lithium/Hydrogen Bonded Complexes Of Trimethylamine, Dimethyl Ether And Dimethyl Sulfide, Salai Cheettu Ammal, P. Venuvanalingam
Ab Initio And Dft Investigations Of Lithium/Hydrogen Bonded Complexes Of Trimethylamine, Dimethyl Ether And Dimethyl Sulfide, Salai Cheettu Ammal, P. Venuvanalingam
Faculty Publications
Ab initio and DFT computations have been carried out on LiF and HF complexes of a set of ndonors viz. trimethylamine, dimethyl ether and dimethyl sulfide with a 631++G(d,p) basis set. The effect of correlation has been included with MP2, MP4 and DFT calculations. NBO analyses of the wavefunctions have been performed to examine the intermolecular interaction at the orbital level. Calculations reveal that these donors form strong n→σ* complexes and computed binding energies of the (CH_{3})_{2}O···HF complex agree very well with the experimental binding energies from IR spectroscopy. LiF forms stronger ...
Ab Initio Study Of Formazan And 3Nitroformazan, G. Buemi, F. Zuccarello, P. Venuvanalingam, M. Ramalingam, Salai Cheettu Ammal
Ab Initio Study Of Formazan And 3Nitroformazan, G. Buemi, F. Zuccarello, P. Venuvanalingam, M. Ramalingam, Salai Cheettu Ammal
Faculty Publications
Formazan and 3nitroformazan have been investigated at abinitio level (MP2/631G** and B3LYP/631G**) in all their possible conformations, for studying the various possibilities of intramolecular hydrogen bonding formation. The transsynscis (TSSC), known also asyellowform, has been found to be the most stable conformer (at least in the gas phase) in both compounds. This particular structure is strongly stabilized by a N–H···N hydrogen bridge, which gives rise to a hexatomic chelate ring, with the possibility of a proton transfer process.This closely resembles that of malondialdehyde, previously studied, in the evolution of ...