Time-dependent Quantum Wave Packet Calculation Research Articles

New diabatic potential energy surfaces of the NaH2 system and dynamics studies for the Na(3p)\u2009+\u2009H2\u2009\u2192\u2009NaH\u2009+\u2009H reaction

The Na(3p) + H2(X1Σg+) → NaH(X1Σ+) + H(2S) reaction plays an important role in the field of diabatic reaction dynamics. A set of new diabatic potential energy surfaces (PESs) of the NaH2 system are structured, which include the diabatic coupling between the lowest two adiabatic states. The electronic structure calculations are performed on the multi-reference configuration interaction level with the cc-pwCVQZ and aug-cc-PVQZ basis sets for Na and H atoms. 32402 geometries are chosen to construct the diabatic data by a unitary transformation based on the molecular property method. The diabatic matrix elements of {{boldsymbol{V}}}_{{bf{11}}}^{{boldsymbol{d}}}, {{boldsymbol{V}}}_{{bf{22}}}^{{boldsymbol{d}}} and {{boldsymbol{V}}}_{{bf{12}}}^{{boldsymbol{d}}} ({{boldsymbol{V}}}_{{bf{21}}}^{{boldsymbol{d}}}) are fitted by the artificial neural network model. The spectroscopic constants of diatoms obtained from the present PESs are consistent with the experimental data. The topographical and intersection characteristics of the {{boldsymbol{V}}}_{{bf{11}}}^{{boldsymbol{d}}} and {{boldsymbol{V}}}_{{bf{22}}}^{{boldsymbol{d}}} surfaces are discussed. Based on the new PESs, the time-dependent quantum wave packet calculations are carried out to study the reaction mechanism of the title reaction in detail.

A time-dependent quantum dynamical study of the C+(2P) + H2(D2,HD) → CH+(CD+) + H(D) reaction

We present time-dependent quantum wave packet calculations for the C+(2P)+H2(D2,HD)→CH+(CD+)+H(D) reactions on the ground 12A′ potential energy surface developed by Li et al. (2015). The reaction probabilities, the integral cross sections and the thermal rate constants were obtained. The calculated thresholds of title reactions agree well with the thermochemical endothermicities. Moreover, the calculated thermal rate constant of C++H2 reaction agrees well with experimental data, however, smaller than the experimental data for the C++HD and C++D2 reactions.

Communication: Creation of molecular vibrational motions via the rotation-vibration coupling.

Building on recent advances in the rotational excitation of molecules, we show how the effect of rotation-vibration coupling can be switched on in a controlled manner and how this coupling unfolds in real time after a pure rotational excitation. We present the first examination of the vibrational motions which can be induced via the rotation-vibration coupling after a pulsed rotational excitation. A time-dependent quantum wave packet calculation for the HF molecule shows how a slow (compared to the vibrational period) rotational excitation leads to a smooth increase in the average bond length whereas a fast rotational excitation leads to a non-stationary vibrational motion. As a result, under field-free postpulse conditions, either a stretched stationary bond or a vibrating bond can be created due to the coupling between the rotational and vibrational degrees of freedom. The latter corresponds to a laser-induced breakdown of the adiabatic approximation for rotation-vibration coupling.

Quantum dynamics study of H + DBr and D + HBr reaction.

Time-dependent quantum wave packet calculations have been performed for the H + DBr and D + HBr reaction using the recent diabatic potential energy surfaces. Reaction probabilities, integral cross sections, and rate constants are obtained. The results show that the isotopic effects have an influence on the nonadiabatic effect which is generally inversely proportional to the atom mass. The calculated rate constants are in good overall agreement with experimental values, indicating that the ab initio surfaces are accurate to describe the isotopic effects.

Time-dependent quantum wave packet and quasiclassical trajectory studies of the Au(2S) + H2(X1∑+g) → AuH(X1∑+g) + H(2S) reaction

The time-dependent quantum wave packet (TDWP) and quasiclassical trajectory calculations (QCT) are carried out for the Au(2S) + H2(X1∑+g) → AuH(X1∑+g) + H(2S) reaction on a global potential energy surface. The reaction probabilities at a series of J values, integral cross sections (ICSs) and differential cross sections of the title reaction are calculated by the TDWP method. For reaction probabilities, there are a mass of sharp oscillations at low collision energy, which can be attributed to resonances supported by the potential well. Due to the endothermicity of the title reaction, the total ICS shows a threshold about 1.53 eV. In order to further investigate the reactive mechanism, the lifetime of complex is calculated by QCT method. At the low collision energy, most intermediate complexes are long lived, which implies that the reaction is governed by indirect reactive mechanism. With the collision energy increasing, the direct reactive mechanism occupies the dominant position. Due to the change of the reactive mechanism, the angular distribution shifts toward the forward direction with collision energy increasing. The isotopic variant, Au + D2→AuD + D reaction, is also calculated by TDWP method. The calculated reaction probabilities and ICSs show that the isotope effect reduces the reactivity.

Theoretical analysis of photoinduced H-atom elimination in thiophenol

The photoinduced hydrogen elimination reaction in thiophenol via the conical intersections of the dissociative (1)πσ∗ excited state with the bound (1)ππ∗ excited state and the electronic ground state has been investigated with ab initio electronic-structure calculations and time-dependent quantum wave-packet calculations. A screening of the coupling constants of the symmetry-allowed coupling modes at the (1)ππ∗-(1)πσ∗ and (1)πσ∗-S(0) conical intersection shows that the SH torsional mode is by far the most important coupling mode at both conical intersections. A model including three intersecting potential-energy surfaces (S(0), (1)ππ∗, (1)πσ∗) and two nuclear degrees of freedom (SH stretch and SH torsion) has been constructed on the basis of ab initio complete-active-space self-consistent field and multireference second-order perturbation theory calculations. The nonadiabatic quantum wave-packet dynamics initiated by optical excitation of the (1)ππ∗ and (1)πσ∗ states has been explored for this three-state two-coordinate model. The photodissociation dynamics is characterized in terms of snapshots of time-dependent wave packets, time-dependent electronic population probabilities, and the branching ratio of the (2)σ/(2)π electronic states of the thiophenoxyl radical. The dependence of the timescale of the photodissociation process and the branching ratio on the initial excitation of the SH stretching and SH torsional vibrations has been analyzed. It is shown that the node structure, which is imposed on the nuclear wave packets by the initial vibrational preparation as well as by the transitions through the conical intersections, has a profound effect on the photodissociation dynamics. The effect of additional weak coupling modes of CC twist (ν(16a)) and ring-distortion (ν(16b)) character has been investigated with three-dimensional and four-dimensional time-dependent wave-packet calculations, and has been found to be minor.

Photochemistry of the water dimer: Time-dependent quantum wave-packet description of the dynamics at the S1-S conical intersection

The photoinduced electron-driven proton-transfer dynamics of the water-dimer system has been investigated by time-dependent quantum wave-packet calculations. The main nuclear degrees of freedom driving the system from the Frank-Condon region to the S(0)-S(1) conical intersection are the distance between the oxygen atoms and the displacement of the hydrogen atom from the oxygen-oxygen bond center. Two important coupling modes have been investigated: Rotation of the H-donating water dangling proton and asymmetric stretching of the H-accepting water dangling protons' O(a)H bonds. Potential energy surfaces of the ground and lowest excited electronic states have been constructed on the basis of ab initio calculations. The time-dependent quantum wave-packet propagation has been employed within the (2 + 1)-dimensional systems for the description of the nonadiabatic dynamics of water dimer. The effects of the initial vibrational state of the system on the electronic population transfer and dissociation dynamics are presented. To approximate the photochemical behavior of water dimer in bulk water, we add a boundary condition into the (2 + 1)-dimensional systems to simulate the existence of water bulk. The results provide insight into the mechanisms of excited state deactivation of the water-dimer system in gas phase and in bulk water through the electron-driven proton-transfer process.

Quantum Dynamics of Br + HD Reaction

In this article we report the results of three-dimensional time-dependent quantum wavepacket calculations carried out for the Br + HD( v = 0, j = 0) reaction in the collision energy range 0.0-1.2 eV. An accurate potential energy surface computed by Kurosaki was used for the dynamical calculations. Both reactive channels, BrH + D and BrD + H, show vibrational enhancement of the reaction cross sections. For the three initial vibrational states considered, the production of BrD channel dominates over that of BrH for the considered collision energy range. The two arrangement channels exhibit different initial rotational state dependence. The cross section for the formation of BrD is almost independent of j whereas the same for the formation of BrH increases with increase in j. A comparison with the results on an e-LEPS surface shows that the two surfaces behave very differently with respect to the cross section for the initial rotational states.

Barrier Height Effect on Cl+H2(D2) Reaction

Three-dimensional time-dependent quantum wave packet calculation was performed to study the reaction dynamics of Cl+H2(D2) on two potential energy surfaces (CW PESs). The first CW PES is with spin-orbit correction; the second is without spin-orbit correction. The integral cross-section and reaction probability as a function of collision energy are calculated in the collision energy range of 0.1 eV to 1.4 eV. For reaction of Cl with D2, the reaction section with spin-orbit correction has a shift toward the high energy because the barrier height increases. As for the reaction of Cl with H2 at low collision energy, it is more reactive on the PES with spin-orbit correction than on the low barrier height PES without spin-orbit correction, due to the tunnel effect for the reaction of the Cl with H2. When the collision energy is higher than 0.7 eV, the reactivity on the low barrier height PES is larger than that on the high barrier height PES. It is believed that the barrier height plays a very important role in the reactivity of Cl with (H2, D2). For the Cl+H2 reaction the barrier width is also very important because of the tunneling effect.

Photoinduced multi-mode quantum dynamics of pyrrole at the [formula omitted]– [formula omitted] conical intersections

The photoinduced dynamics of pyrrole at the A 1 2 ( π σ ∗ ) – S 0 and B 1 1 ( π σ ∗ ) – S 0 conical intersections has been investigated by multi-mode time-dependent quantum wave-packet calculations. Diabatic potential-energy surfaces have been constructed for both conical intersection using accurate multi-reference ab initio electronic-structure calculations. In addition to the NH stretching coordinate, the three (four) symmetry-allowed coupling modes of A 2 ( B 1 ) symmetry have been considered for the A 1 2 ( π σ ∗ ) – S 0 ( B 1 ( π σ ∗ ) – S 0 ) conical intersections. Wave-packet dynamics calculations have been performed for three-dimensional models, taking account of the two dominant coupling modes of each conical intersection. The electronic population-transfer processes at the conical intersections, the branching ratio for the dissociation to the ground and excited states of the pyrrolyl radical, and their dependence on the initial preparation of the system have been investigated. It is shown that the excitation of the NH stretching mode strongly enhances the photodissociation rate, while the excitation of the strongest coupling mode has a pronounced effect on the branching ratio of the photodissociation process. Although the inclusion of the second (weaker) coupling mode has little effect on the electronic population dynamics, it leads to interesting changes of the nodal pattern of the wave packet at the conical intersections. The calculations provide insight into the effect of the multiple coupling modes on the process of direct photodissociation through a conical intersection.

Quantum Wave Packet Studies on F + HBr Reaction

Time-dependent quantum wave packet calculations were carried out for the F + HBr reaction on the latest London-Erying-Polanyi-Sato potential energy surface constructed by Persky et al. The calculated reaction probabilities dramatically increase near the zero collision energy and then slightly decrease with increasing collision energy, which corresponds well to the behavior of a barrierless reaction. The effects of reagent HBr excitation were examined, it is shown that both the vibrational and the rotational excitations of reagent HBr have a negative effect on the reactivity of F + HBr. The integral cross-section for the ground state of the reagent HBr decreases at a low collision energy and then becomes plat with increasing collision energy, which is reasonable for the feasibility of such an exothermal reaction. The rate constant that was obtained is slightly higher than that obtained in the quasi-classical trajectory calculation.

STRONG VIBRATIONAL ENHANCEMENT OF SUBSTANTIALLY ENDOTHERMIC REACTION K + HF: A TIME-DEPENDENT QUANTUM WAVE PACKET STUDY

Detailed dynamics of the substantially endothermic reaction K + HF on a new ab initio ground potential energy surface has been studied by means of time-dependent quantum wave packet calculation. The calculations showed that the reaction could be significantly enhanced by vibrational excitation of HF , but not very sensitive to initial rotational excitation. The relative and absolute integral cross sections and the logarithm of the σ(v = 1)/σ(v = 0) ratio have been calculated and compared with available experimental and theoretical results. Relatively good agreement with experiment and other calculations was obtained. Reaction rate constants of this reaction was also calculated and discussed.

Photochemistry of pyrrole: Time-dependent quantum wave-packet description of the dynamics at the π1σ*-S conical intersections

The photoinduced hydrogen-elimination reaction in pyrrole via the conical intersections of the two (1)pi sigma(*) excited states with the electronic ground states [(1)B(1)(pi sigma(*))-S(0) and (1)A(2)(pi sigma(*))-S(0)] have been investigated by time-dependent quantum wave-packet calculations. Model potential-energy surfaces of reduced dimensionality have been constructed on the basis of accurate multireference ab initio electronic-structure calculations. For the (1)B(1)-S(0) conical intersection, the model includes the NH stretching coordinate as the tuning mode and the hydrogen out-of-plane bending coordinate as the coupling mode. For the (1)A(2)-S(0) conical intersection, the NH stretching coordinate and the screwing coordinate of the ring hydrogens are taken into account. The latter is the dominant coupling mode of this conical intersection. The electronic population-transfer processes at the conical intersections, the branching ratio between the dissociation channels, and their dependence on the initial preparation of the system have been investigated for pyrrole and deuterated pyrrole. It is shown that the excitation of the NH stretching mode strongly enhances the reaction rate, while the excitation of the coupling mode influences the branching ratio of different dissociation channels. The results suggest that laser control of the photodissociation of pyrrole via mode-specific vibrational excitation should be possible. The calculations provide insight into the microscopic details of ultrafast internal-conversion processes in pyrrole via hydrogen-detachment processes, which are aborted at the (1)pi sigma(*)-S(0) conical intersections. These mechanisms are of relevance for the photostability of the building blocks of life (e.g., the DNA bases).

THE FAILURE OF CS APPROXIMATION IN QUANTUM REACTION SCATTERING WITH DOUBLE DEEP WELL: TIME-DEPENDENT CALCULATION FOR O + NH REACTION

The present paper shows the failure of CS (centrifugal sudden or coupled states) approximation in the time-dependent (TD) quantum wave packet calculation for the exoergicity reaction O + NH on the 1A′ potential energy surface [Guadagnini, Schatz and Walch, J Chem Phys102:774 (1995)] that has double deep wells. In order to show this, total reaction probabilities and rate constants for the title reaction are presented in this study with the CS approximation and the CC (close-coupling) method, respectively. The results show that by carrying out the wave packet propagation to several picoseconds with the CC method, we can resolve all the resonance features for the title reaction and the differences between the CS and the CC become larger as J becomes larger. When J becomes larger the agreement between the CS and the CC gets progressively worse. The failure of the CS approximation can be explained with the results of double deep wells, which cause long propagation time and make the coupling of K states important.

Time-dependent quantum wave-packet description of the π1σ* photochemistry of phenol

The photoinduced hydrogen elimination reaction in phenol via the conical intersections of the dissociative π1σ* state with the π1π* state and the electronic ground state has been investigated by time-dependent quantum wave-packet calculations. A model including three intersecting electronic potential-energy surfaces (S0, π1σ*, and π1π*) and two nuclear degrees of freedom (OH stretching and OH torsion) has been constructed on the basis of accurate ab initio multireference electronic-structure data. The electronic population transfer processes at the conical intersections, the branching ratio between the two dissociation channels, and their dependence on the initial vibrational levels have been investigated by photoexciting phenol from different vibrational levels of its ground electronic state. The nonadiabatic transitions between the excited states and the ground state occur on a time scale of a few tens of femtoseconds if the π1π*-π1σ* conical intersection is directly accessible, which requires the excitation of at least one quantum of the OH stretching mode in the π1π* state. It is shown that the node structure, which is imposed on the nuclear wave packet by the initial preparation as well as by the transition through the first conical intersection (π1π*-π1σ*), has a profound effect on the nonadiabatic dynamics at the second conical intersection (π1σ*-S0). These findings suggest that laser control of the photodissociation of phenol via IR mode-specific excitation of vibrational levels in the electronic ground state should be possible.

Femtosecond study of Cu(H2O) dynamics

The short-time nuclear dynamics of Cu(H(2)O) is investigated using femtosecond photodetachment-photoionization spectroscopy and time-dependent quantum wave packet calculations. The Cu(H(2)O) dynamics is initiated in the electronic ground state of the complex by electron photodetachment from the Cu(-)(H(2)O) complex, where hydrogen atoms are oriented toward Cu. Several time-resolved resonant multiphoton ionization schemes are used to probe the ensuing reorientation and dissociation. Immediately following photodetachment, the neutral complex is far from its minimum energy geometry and possesses an internal energy comparable to the Cu-H(2)O dissociation energy and undergoes both large-amplitude H(2)O motion and dissociation. Dissociation is observed to occur on three distinct time scales: 0.6, 8, and 100 ps. These results are compared to the results of time-dependent J=0 wave packet calculations, propagating the initial anion vibrational wave functions on the ground-state potential of the neutral complex. An excellent agreement is obtained between the experimental results and the ionization signals derived from the calculated probability amplitudes. Related experiments and calculations are carried out on the Cu(D(2)O) complex, with results very similar to those of Cu(H(2)O).

Quantum scattering calculation of the O(1D)+HBr reaction.

Three-dimensional time-dependent quantum wave packet calculation for the O((1)D)+HBr reaction has been carried out using an accurate ab initio global potential energy surface [K. A. Peterson, J. Chem. Phys. 113, 4598 (2000)]. The calculations show that the initial state-selected reaction probabilities are dominated by resonance structures, and the lifetime of the resonance is generally in the subpicosecond time scale. The energy dependence of the reaction cross section is computed, which manifests still resonance structures, and is a decreasing function of the translational energy. The thermal rate constants are also computed, which are nearly independent on the temperature. The calculation results are discussed and compared to similar reaction with deep well.

Time-dependent quantum wave packet calculation for nonadiabatic F(2P3/2,2P1/2)+H2 reaction

In this paper we present a time-dependent quantum wave packet calculation for the reaction of F(2P3/2,2P1/2)+H2 on the Alexander–Stark–Werner potential energy surface. The reaction probabilities and the integral cross sections for the reaction of F(2P3/2,2P1/2)+H2 (v=j=0) are computed using time-dependent quantum methods with the centrifugal sudden approximate. The results are compared with recent time-independent quantum calculations. The two-surface reaction probability for the initial ground spin–orbit state of J=0.5 is similar to the time-independent result obtained by Alexander et al. [J. Chem. Phys. 113, 11084 (2000)]. Our calculation also shows that electronic coupling has a relatively minor effect on the reactivity from the P3/22 state but a non-negligible one from the P1/22 state. By comparison with exact time-independent calculations, it is found that the Coriolis coupling plays a relatively minor role. In addition, most of the reactivity of the excited state of fluorine atom results from the spin–orbit coupling.

Reactivity of the Ground and Excited Spin−Orbit States for the Reaction of the F(2P3/2,2P1/2) with D2

In this paper, we present a time-dependent quantum wave packet calculation based on the Alexander−Stark−Werner (ASW) potential energy surfaces (PESs) to study the reactivity of the ground and excited spin−orbit states for the reaction of F(2P3/2,2P1/2) with D2 (v = j = 0). The reaction probabilities and the integral cross sections are calculated. Furthermore, the multistate cross sections are compared with the single-state calculation. The multistate cross section is smaller than the single-state calculation at higher collision energy. The effect of the nonadiabatic coupling becomes more and more obvious as the collision energy increases. The overall reactivity of the excited state of F is, at most, 25% of that of the ground spin−orbit states. The threshold energy of the F(2P3/2) + D2 reaction is ∼0.10 kcal/mol. The contributions of the excited state of F are 0.9% and 3.1% of the total average rate constant, at 200 and 500 K, respectively. The effect of the excited spin−orbit state rate constant to the average rate constant is very small but grows slowly as the temperature increases.

Quantum Dynamics Study of Torsional Excitation of Glycine in Collision with Hydrogen Atom on ab Initio Potential Energy Surface

Quantum mechanical study has been carried out to investigate C−C torsional excitation in glycine via collisional energy transfer with hydrogen atom. In this study, ab initio calculation is carried out to generate potential energies on a two-dimensional grid (torsional angle and radial coordinate) for given fixed orientational angle (θ, φ). These discrete energies are fitted with a local linear least-squares method to generate potential energies at any given point in two-dimensional space for dynamics calculation. Time-dependent quantum wave packet calculation is employed to study energy transfer to the C−C torsional mode of glycine, and state-to-state transition probabilities are obtained for different initial angles of collision. Strong angle-dependent energy transfer is observed from the calculation. Although the total energy transferred to the torsional mode is small, collision from certain angles can result in relatively large conformational change in torsion by as much as 30° degrees.