The influence of molecular alignment and orientation in the ground state and excited state on the resonance-enhanced multi-photon ionization dynamics.

We explore the influence of molecular alignment and orientation in the ground and excited states on the ionization probability, photoelectron angular distribution (PAD), energy-resolved photoelectron energy spectrum (PES) and two-dimensional momentum spectrum in the resonance-enhanced multiphoton ionization (REMPI) process. The calculated results for the LiH molecule show that molecular pre-alignment and -orientation have different effects on molecular photoionization. The ionization probability and energy-resolved photoelectron spectrum are associated with molecular pre-alignment. The angular distribution of photoelectrons and angular distribution of the momentum spectra are closely dependent on molecular pre-orientation. The ionization probability is also related to the center time and overlap area of the pump and probe pulses.

Formation of ultracold 39K133Cs molecules via Feshbach optimized photoassociation.

A Feshbach optimized photoassociation (FOPA) process for preparing ultracold excited-state 39K133Cs molecules is studied theoretically. Under the joint action of the magnetic field and short laser pulse, the colliding atoms in a superposition state composed of eight hyperfine components are converted into a molecule in the vibrational level of the excited state via two transition processes, the transition between singlet states and the transition between triplet states. The association efficiency can be significantly enhanced by taking advantage of Feshbach resonance. At different resonance positions, different hyperfine components of the superposition state dominate over the FOPA process, and the quantum interference displays different behaviors. Compared with the FOPA process only including a single hyperfine component, the quantum interference in the FOPA process containing all hyperfine components has a visible effect on the association efficiency.

The modulating action of electric field on magnetically tuned Feshbach resonance.

We investigate the modulating action of an external electric field on the magnetically tuned Feshbach resonance in ultracold heteronuclear atomic collision by using the multichannel quantum-defect theory (MQDT). The coupling between different partial wave states induced by an electric field is included into the singlet and triplet quantum defect matrices y(0) and y(1). By taking the truncated -C6/R6 - C8/R8 - C10/R10 potential as the reference potential, the threshold behaviors of four quantum-defect parameters for the lowest three partial waves are described. The results calculated by using the MQDT agree with those calculated using the coupled channel method. Moreover, we present an analytical expression used for describing the variation of the position and width of the magnetically tuned Feshbach resonance modulated by an electric field.

The photoionization dynamics based on molecular pre-orientation.

We study theoretically the photoionization dynamics of pre-oriented NaK molecule. Firstly, a THz laser pulse is utilized to orient the ground state molecule. And then the pump and probe laser pulses are used to excite and ionize the molecule, respectively. We study the influence of molecular orientation duration and degree on the ionization probability, angle-resolved photoelectron spectrum and photoelectron angular distribution (PAD). It is shown that we could obtain more stable ionization signal and PAD when the molecules are ionized in molecular orientation duration. We could increase the ionization probability and obtain more concentrated ionization signal and photoelectron distribution by increasing the orientation degree in the ground state. Moreover, we discuss the splitting pattern in the angle-resolved photoelectron spectrum.

Theoretical insights into excited-state intramolecular and multiple intermolecular hydrogen bonds in 2-(2-Hydroxy-phenyl)-4(3H)-quinazolinone.

The photophysical properties and photochemistry reactions of 2-(2-Hydroxy-phenyl)-4(3H)-quinazolinone (HPQ) system in different solutions are studied by using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. Our theoretical investigation explores that an ultrafast barrier-free excited state intramolecular proton transfer (ESIPT) process occurs and the configuration twisting is found in the electronic excited state. In the polar protic methanol solution, the hydrogen-bonded complex composed by HPQ and two methanol molecules (HPQ-2M) could exist stably in the ground state. Upon photoexcitation the isolated HPQ is initially excited to the first excited state, while the HPQ-2M system is firstly excited to the S3 state and undergoes internal conversion (IC) to the S1 state. The intermolecular hydrogen bonds are strengthened in the excited state. The simulated electronic spectra agree well with the experimental results. The strengthening of the intermolecular hydrogen bonds is also confirmed by the calculated vibrational spectra. In addition, the intramolecular charge transfer happens in both HPQ and HPQ-2M systems from the frontier molecular orbital analysis.

High-rank separable atom-atom interaction potential used for solving two-body Lippmann-Schwinger and three-body Faddeev equations.

We derive a high-rank separable potential formula of the atom-atom interaction by using the two-body wave function in the coordinate space as inputs. This high-rank separable potential can be utilized to numerically solve the two-body Lippmann-Schwinger equation and three-body Faddeev equation. By analyzing the convenience and stability of numerical calculations for different kinds of the matrix forms of the Lippmann-Schwinger and Faddeev equations, we can find the optimal forms of the kernal matrices in the two- and three-body scattering equations. We calculate the dimer bound energy, two-body scattering phase shift and off-shell t-matrix, the trimer bound energy, atom-dimer scattering length, and three-body recombination rate using the high-rank separable potentials, taking the identical 4He atoms as an application example. All the calculations converge quickly for the rank number N ⩾ 3 . The high-rank separable potential is valid for two-body scattering calculation of 4He atoms, but not accurate enough for reproducing the three-body scattering results by using only two-body s-wave interaction and describing the contributions of two-body high partial-waves to the three-body scattering for the 4He3 system.

Accurate calculations of weakly bound state energy and scattering length near magnetically tuned Feshbach resonance using the separable potential method.

We present a theoretical model for investigating the magnetically tuned Feshbach resonance (MTFR) of alkali metal atoms using the separable potential method (SPM). We discuss the relationship and difference between the SPM and the asymptotic bound state model. To demonstrate the validity of the SPM, we use it to calculate the weakly bound state energy and magnetically tuned scattering length for the 6Li-40K, 7Li2, and 6Li2 systems with narrow and broad Feshbach resonances. The results of the SPM calculations are in good agreement with those of coupled channel calculations and with experimental measurements for all three systems. The SPM, by simplifying the calculation of the two-body MTFR, is expected to simplify numerical computations for three-atom collisions in a magnetic field and the Feshbach-optimized photoassociation process.

Cold atom-atom-ion three-body recombination of 4He-4He-X- (X = H or D).

The atom-atom-ion three-body recombination (TBR) of mixed 4He and X- (X = H or D) systems is investigated by solving the Schrödinger equation using the adiabatic hyperspherical representation method. It is shown that the dominant products after a TBR in the ultracold limit (E ≤ 0.1 mK × kB) are different for the two systems. For the 4He4HeH- system, the rate of TBR into the 4HeH- ion is nearly two orders of magnitude larger than that of TBR into the neutral 4He2 molecule. In contrast, the yield of 4He2 is a little higher than that of 4HeD- for the 4He4HeD- system. Furthermore, since the adiabatic potentials become more attractive and the nonadiabatic couplings become much stronger by substituting D for H in the 4He4HeH- system, the total TBR rate for the 4He4HeD- system is nearly two orders of magnitude larger than that for the 4He4HeH- system.

Role of sharp avoided crossings in short hyper-radial range in recombination of the cold 4He3 system.

The role of sharp avoided crossings (SACs) in a short hyper-radial range R≤ 50 a.u. in the calculation of recombination for a cold 4He3 system is investigated in the adiabatic hyperspherical representation by "turning off and on" the relevant nonadiabatic couplings. The influence of SACs on the recombination is related with the channels of the system and with the scattering energy. For JΠ = 0+ symmetry, the two-body recombination channel has an attractive potential well, which makes radial wave functions of both two-body recombination channel and three-body continuum channels accessible in the short hyper-radial range where SACs are located. The SACs consequently play an important role in coupled-channel calculations and this is particularly the case for lower scattering energies. However, for excited nuclear orbital momenta, i.e., JΠ = 1-, 2+,…, 7- symmetries, the two-body recombination channel has a repulsive interaction and the radial wave functions are not accessible in the short hyper-radial range. Therefore, omission of SACs in the short range for these symmetries has no effect on the numerical results, which leads to great savings on hyper-radial grid points in the practical numerical calculations. Moreover, to make the nonadiabatic couplings among channels to be continuous in the hyper-radius, different methods associated with the application of consistent phase convention are discussed.

Molecular alignment effect on the photoassociation process via a pump-dump scheme.

The photoassociation processes via the pump-dump scheme for the heternuclear (Na + H → NaH) and the homonuclear (Na + Na → Na2) molecular systems are studied, respectively, using the time-dependent quantum wavepacket method. For both systems, the initial atom pair in the continuum of the ground electronic state (X(1)Σ(+)) is associated into the molecule in the bound states of the excited state (A(1)Σ(+)) by the pump pulse. Then driven by a time-delayed dumping pulse, the prepared excited-state molecule can be transferred to the bound states of the ground electronic state. It is found that the pump process can induce a superposition of the rovibrational levels |v, j〉 on the excited state, which can lead to the field-free alignment of the excited-state molecule. The molecular alignment can affect the dumping process by varying the effective coupling intensity between the two electronic states or by varying the population transfer pathways. As a result, the final population transferred to the bound states of the ground electronic state varies periodically with the delay time of the dumping pulse.

Optimal control of charge transfer for slow H+ + D collisions with shaped laser pulses.

We show that optimally shaped laser pulses can beneficially influence charge transfer in slow H(+)+D collisions. Time-dependent wave packet optimal control simulations are performed based on a two-state adiabatic Hamiltonian. Optimal control is performed using either an adaptive or a fixed target to obtain the desired laser control field. In the adaptive target scheme, the target state is updated according to the renormalized fragmentary yield in the exit channel throughout the optimization process. In the fixed target scheme, the target state in the exit channel is a normalized outgoing Gaussian wave packet located at a large internuclear separation. Both approaches produced excellent optimal outcomes, far exceeding that achieved in the field-free collisional charge transfer. The adaptive target scheme proves to be more efficient, and often with complex final wave packet. In contrast, the fixed target scheme, although more slowly convergent, is found to produce high fidelity for the desired target wave packet. The control mechanism in both cases utilizes bound vibrational states of the transient HD(+) complex.

Intermolecular hydrogen bond and twisted intramolecular charge transfer in excited state of fast violet B (FVB) in methanol solution.

The excited state hydrogen bonding dynamics and corresponding photophysical processes of fast violet B (FVB) in hydrogen-donating methanol (MeOH) solution are investigated by using time-dependent density functional theory (TDDFT) method. In the FVB molecule, there are -C=O, -N-H groups which could act as hydrogen acceptor and donor. It is demonstrated that both the intramolecular hydrogen bond O⋯H-N in FVB and intermolecular hydrogen bond C=O⋯H-O between FVB and MeOH are formed in the ground state S0 and strengthened in the excited state S1. The absorption spectra are obviously red shifted for the hydrogen-bonded complex in comparison with FVB monomer in the low energy range. The theoretical investigation demonstrates that the twisted intramolecular charge transfer takes place in the excited states for both isolated FVB and hydrogen-bonded complex, and the dominant twisting is along N2-C3 bond. The potential energy curve is investigated to understand the photophysics process of FVB and hydrogen-bonded complex.

The influence of field-free orientation on the predissociation dynamics of the NaI molecule.

The orientation and predissociation dynamics of the NaI molecule are studied by using a time-dependent wavepacket method. The NaI molecule is first pre-oriented by a single-cycle pulse (SCP) in terahertz (THz) region and then predissociated by a femtosecond pump pulse. The influence of the molecular field-free orientation on the predissociation dynamics is studied in detail. We calculate the radial and angular distributions, the molecular orientation degrees, and the time-dependent populations for both the ground and excited electronic states. It is found that the pre-orientation affects the angular distributions significantly, and that it has weak influence on the radial distributions. By varying the delay time between the THz SCP and the pump pulse, the angular distribution of the fragments from the predissociation can be manipulated.

Field-free orientation by a single-cycle THz pulse: the NaI and IBr molecules.

The field-free orientation induced by a single-cycle terahertz (THz) laser pulse is studied for two "heavy" molecules, NaI and IBr. Two methods are used and compared in the calculations: One is to solve the exact time-dependent Schrödinger equation (ETDSE) considering the full-rovibrational degrees of freedom, and the other is to invoke the rigid-rotor approximation (RRA). Calculations are performed for the central frequency varying from 0.05 to 1.0 THz and for the peak intensity taken to be 5 × 10(7), 2 × 10(8), and 5 × 10(8) W∕cm(2), respectively. The degree of field-free orientation, , is strongly dependent on the central frequency and the peak intensity of the single-cycle THz pulse. The maximum degree of field-free orientation is determined to be 0.84 for NaI and 0.63 for IBr in these given ranges of frequency and intensity. The molecular orientation obtained by the RRA calculations is in good agreement with that obtained by the ETDSE in the given parameter region.

Multiple hydrogen bonding in excited states of aminopyrazine in methanol solution: time-dependent density functional theory study.

Aminopyrazine (AP) and AP-methanol complexes have been theoretically studied by using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The excited-state hydrogen bonds are discussed in detail. In the ground state the intermolecular multiple hydrogen bonds can be formed between AP molecule and protic solvents. The AP monomer and hydrogen-bonded complex of AP with one methanol are photoexcited initially to the S2 state, and then transferred to the S1 state via internal conversion. However the complex of AP with two methanol molecules is directly excited to the S1 state. From the calculated electronic excited energies and simulated absorption spectra, we find that the intermolecular hydrogen bonds are strengthened in the electronic excited states. The strengthening is confirmed by the optimized excited-state geometries. The photochemical processes in the electronic excited states are significantly influenced by the excited-state hydrogen bond strengthening.

Quantum control of multi-photon dissociation of HCl+ with intense femtosecond laser pulses.

The multi-photon dissociation of HCl(+) through three channels HCl(+)→H(1s|(2)S)+Cl(+)((3)P), H(+)+Cl((2)P(0)), and H((2)S)+Cl(+)((1)D) steered by intense femtosecond laser pulses are investigated theoretically using the quantum wave packet dynamics. The numerical calculations are performed in two cases without and with the coupling between the excited states. The results show that the dissociation is sensitive to the duration τ, peak intensity I(0), and the resonance of driving laser fields. In the case without the coupling, the effect of the permanent dipole moments on the dissociations dominates for τ < 15 fs, while with the increase of τ, the dissociation dynamics is mainly dominated by the transition dipole moment. In the case with the coupling, the above-threshold dissociation process is complex, and the non-resonant (λ = 400 nm) and resonant (λ = 800 and 1200 nm) laser fields lead to different variation of the branching ratios. The angle-resolved energy distribution is also discussed in detail.

Field-free molecular orientation with terahertz few-cycle pulses.

We demonstrate theoretically an efficient field-free orientation in LiH and LiCl driven by available terahertz few-cycle pulses (TFCPs). Exact results by numerically solving the time-dependent Schrodinger equation including the vibrational and rotational degrees of freedom are compared to the rigid-rotor approximation (RRA) as well as to the impulsive approximation (IA), and the effect of rotational-vibrational coupling on the both RRA and IA is examined in detail. We find that the current available TFCPs may overcome the technical limitation of terahertz half-cycle pulse for enhancing the field-free molecular orientation.

Determination of the phase of terahertz few-cycle laser pulses.

We propose an approach to determine the carrier-envelope phase (CEP) of a terahertz few-cycle pulse by observing the field-free molecular orientation. We find that the degree of orientation sensitively depends on the CEP, providing a new route for measuring the CEP without phase ambiguity. By taking advantage of the field-free molecular orientation, an important effect of the CEP drift caused by the dephasing of the generating medium on the accurate measurement of the CEP value is eliminated.

Control of photodissociation and photoionization of the NaI molecule by dynamic Stark effect.

The diabatic photodissociation and photoionization processes of the NaI molecule are studied theoretically using the quantum wave packet method. A pump laser pulse is used to prepare a dissociation wave packet that propagates through both the ionic channel (NaI-->Na(+)+I(-)) and the covalent channel (NaI-->Na+I). A Stark pulse is used to control the diabatic dissociation dynamics and a probe pulse is employed to ionize the products from the two channels. Based on the first order nonresonant nonperturbative dynamic Stark effect, the dissociation probabilities and the branching ratio of the products from the two channels can be controlled. Moreover the final photoelectron kinetic energy distribution can also be affected by the Stark pulse. The influences of the delay time, intensity, frequency, and carrier-envelope phase of the Stark pulse on the dissociation and ionization dynamics of the NaI molecule are discussed in detail.

Steering dissociation of Br2 molecules with two femtosecond pulses via wave packet interference.

The dissociation dynamics of Br2 molecules induced by two femtosecond pump pulses are studied based on the calculation of time-dependent quantum wave packet. Perpendicular transition from X 1Sigma g+ to A 3Pi 1u+ and 1Pi 1u+ and parallel transition from X 1Sigma g+ to B 3Pi 0u+, involving two product channels Br (2P3/2)+Br (2P3/2) and Br (2P3/2)+Br* (2P1/2), respectively, are taken into account. Two pump pulses create dissociating wave packets interfering with each other. By varying laser parameters, the interference of dissociating wave packets can be controlled, and the dissociation probabilities of Br2 molecules on the three excited states can be changed to different degrees. The branching ratio of Br*/(Br+Br*) is calculated as a function of pulse delay time and phase difference.