Fewest switches surface hopping with Baeck-An couplings

In the Baeck-An (BA) approximation, first-order nonadiabatic coupling vectors are given in terms of adiabatic energy gaps and the second derivative of the gaps with respect to the coupling coordinate. In this paper, a time-dependent (TD) BA approximation is derived, where the couplings are computed from the energy gaps and their second time-derivatives. TD-BA couplings can be directly used in fewest switches surface hopping, enabling nonadiabatic dynamics with any electronic structure methods able to provide excitation energies and energy gradients. Test results of surface hopping with TD-BA couplings for ethylene and fulvene show that the TD-BA approximation delivers a qualitatively correct picture of the dynamics and a semiquantitative agreement with reference data computed with exact couplings. Nevertheless, TD-BA does not perform well in situations conjugating strong couplings and small velocities. Considered the uncertainties in the method, TD-BA couplings could be a competitive approach for inexpensive, exploratory dynamics with a small trajectories ensemble. We also assessed the potential use of TD-BA couplings for surface hopping dynamics with time-dependent density functional theory (TDDFT), but the results are not encouraging due to singlet instabilities near the crossing seam with the ground state.

Constructing Spin-Adiabatic States for the Modeling of Spin-Crossing Reactions I. A Shared-Orbital Implementation

In the modeling of spin-crossing reactions, it has become popular to directly explore the spin-adiabatic surfaces. Specifically, through constructing spin-adiabatic states from a two-state Hamiltonian (with spin-orbit coupling matrix elements) at each geometry, one can readily employ advanced geometry optimization algorithms to acquire a “transition state" structure, where the spin crossing occurs. In this work, we report the implementation of a fully variational spin-adiabatic approach based on Kohn-Sham density functional theory spin states (sharing the same set of molecular orbitals) and the Breit-Pauli one-electron spin-orbit operator. For three model spin-crossing reactions [predissociation of N2O, singlet-triplet conversion in CH2, and CO association to Fe(CO)4], the spin-crossing points were easily obtained. Our results also indicated the Breit-Pauli one-electron spin-orbit coupling can vary significantly along the reaction pathway on the spin-adiabatic energy surface. On the other hand, due to the restriction that low-spin and high-spin states share the same set of molecular orbitals, the acquired spin-adiabatic energy surface shows a cusp (i.e. a first-order discontinuity) at the crossing point, which prevents the use of standard geometry optimization algorithms to pinpoint the crossing point. An extension with this restriction removed is being developed to achieve the smoothness of spin-adiabatic surfaces.

Constructing Spin-Adiabatic States for the Modeling of Spin-Crossing Reactions I. A Shared-Orbital Implementation

In the modeling of spin-crossing reactions, it has become popular to directly explore the spin-adiabatic surfaces. Specifically, through constructing spin-adiabatic states from a two-state Hamiltonian (with spin-orbit coupling matrix elements) at each geometry, one can readily employ advanced geometry optimization algorithms to acquire a “transition state" structure, where the spin crossing occurs. In this work, we report the implementation of a fully variational spin-adiabatic approach based on Kohn-Sham density functional theory spin states (sharing the same set of molecular orbitals) and the Breit-Pauli one-electron spin-orbit operator. For three model spin-crossing reactions [predissociation of N2O, singlet-triplet conversion in CH2, and CO association to Fe(CO)4], the spin-crossing points were easily obtained. Our results also indicated the Breit-Pauli one-electron spin-orbit coupling can vary significantly along the reaction pathway on the spin-adiabatic energy surface. On the other hand, due to the restriction that low-spin and high-spin states share the same set of molecular orbitals, the acquired spin-adiabatic energy surface shows a cusp (i.e. a first-order discontinuity) at the crossing point, which prevents the use of standard geometry optimization algorithms to pinpoint the crossing point. An extension with this restriction removed is being developed to achieve the smoothness of spin-adiabatic surfaces.

Constructing Spin-Adiabatic States for the Modeling of Spin-Crossing Reactions I. A Shared-Orbital Implementation

In the modeling of spin-crossing reactions, it has become popular to directly explore the spin-adiabatic surfaces. Specifically, through constructing spin-adiabatic states from a two-state Hamiltonian (with spin-orbit coupling matrix elements) at each geometry, one can readily employ advanced geometry optimization algorithms to acquire a “transition state" structure, where the spin crossing occurs. In this work, we report the implementation of a fully variational spin-adiabatic approach based on Kohn-Sham density functional theory spin states (sharing the same set of molecular orbitals) and the Breit-Pauli one-electron spin-orbit operator. For three model spin-crossing reactions [predissociation of N2O, singlet-triplet conversion in CH2, and CO association to Fe(CO)4], the spin-crossing points were easily obtained. Our results also indicated the Breit-Pauli one-electron spin-orbit coupling can vary significantly along the reaction pathway on the spin-adiabatic energy surface. On the other hand, due to the restriction that low-spin and high-spin states share the same set of molecular orbitals, the acquired spin-adiabatic energy surface shows a cusp (i.e. a first-order discontinuity) at the crossing point, which prevents the use of standard geometry optimization algorithms to pinpoint the crossing point. An extension with this restriction removed is being developed to achieve the smoothness of spin-adiabatic surfaces.

Design and Implementation of Low Power Multiplier Using Proposed Two Phase Clocked Adiabatic Static CMOS Logic Circuit

<p class="Abstract">This paper presents a design and implementation of 2*2 array and 4*4 array multiplier using proposed Two Phase Clocked Adiabatic Static CMOS logic (2PASCL) circuit. The proposed 2PASCL circuit is based on adiabatic energy recovery principle which consumes less power. The proposed 2PASCL uses two sinusoidal power clocks which are 1800 phase shifted with each other. The measurement result of 2*2 array proposed 2PASCL multiplier gives 80.16 % and 97.67 %power reduction relative to reported 2PASCL and conventional CMOS logic and the measurement result of 4*4 array proposed 2PASCL multiplier demonstrate 32.88 % and 82.02 %power reduction compared to reported 2PASCL and conventional CMOS logic . Another advantage of the proposed circuit is that it gives less power though the number of transistor in proposed and reported 2PASCL circuit is same. From the result we conclude that proposed 2PASCL technology is advantageous to application in low power digital systems, pacemakers and sensors. The circuits are simulated at 180nm technology mode.</p>

Direct diabatization based on nonadiabatic couplings: the N/D method

We propose a new diabatization method that is direct, orbital-free, and adiabatic-equivalent based on directly calculated nonadiabatic couplings of states and the adiabatic energy gradients.