Photoswitching of Salicylidene Methylamine: A Theoretical Photodynamics Study

Spörkel, Lasse; Jankowska, Joanna; Thiel, Walter

doi:10.1021/jp5095678

Cited by 42 publications

(53 citation statements)

References 62 publications

(85 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[30][31][32][33][34][35][36] Among the most frequently used Hartree-Fock based zero-differential overlap (ZDO) methods are PM6, [37][38][39][40][41][42] -used for the computation of ground state structures and energies [43][44][45][46] -and OM2, [47][48][49][50][51] which is extensively applied in excited state dynamics studies. [52][53][54][55][56] Over the past decades, density functional tight binding (DFTB) methods, [57][58][59][60][61][62][63][64][65][66] as derived from DFT, have found more attention, whereat in recent years the extended tightbinding (xTB) family of methods has been developed. This xTB class of methods is especially developed for the reasonable calculation of Geometries, Non-covalent interactions, and vibrational Frequencies (GFN).…”

Section: Introductionmentioning

confidence: 99%

A Robust Non-Self-Consistent Tight-Binding Quantum Chemistry Method for large Molecules

Pracht

Caldeweyher²,

Ehlert³

et al. 2019

Preprint

106

View full text Add to dashboard Cite

We propose a semiempirical quantum chemical method, designed for the fast calculation of molecular Geometries, vibrational Frequencies and Non-covalent interaction energies (GFN) of systems with up to a few thousand atoms. Like its predecessors GFN-xTB and GFN2-xTB, the new method termed GFN0-xTB is parameterized for all elements up to radon (Z = 86) and mostly shares well-known density functional tight-binding approximations as well as basis set and integral approximations. The main new feature is the avoidance of the self-consistent charge iterations leading to speed-ups of a factor of 2-20 depending on the size and electronic complexity of the system. This is achieved by including only quantum mechanical contributions up to first-order which are incorporated similar to the previous versions without any pair-specific parameterization. The essential electrostatic electronic interaction is treated by a classical electronegativity equilibration charge model yielding atomic partial charges that enter the electronic Hamiltonian indirectly. Furthermore, the atomic charge-dependent D4 dispersion correction is included to account for long range London correlation effects. Formulas for analytical total energy gradients with respect to nuclear displacements are derived and implemented in the xtb code allowing numerically very precise structure optimizations. The neglect of self-consistent energy terms not only leads to a large gain in computational speed but also can increase robustness in electronically difficult situations because ill-convergence or artificial charge-transfer (CT) is avoided. The comparison of GFN0-xTB and GFN/GFN2-xTB allows dissection of quantum electronic polarization and CT effects thereby improving our understanding of chemical bonding. Compared the the most sophisticated multipole-based GFN2-xTB model (which approaches DFT accuracy for the target properties closely), GFN0-xTB performs slightly worse for non-covalent interactions and molecular structures, while very good results are observed for conformational energies. Vibrational frequencies are obtained less accurately than with GFN/GFN2-xTB but they may still be useful for various purposes like estimating relative thermostatistical reaction energies. Most exceptional is the fact that even relatively complicated transition metal complex structures can be accurately optimized with a non-self-consistent quantum approach. The new method bridges the gap between force-fields and traditional semiempirical methods with its excellent computational cost to accuracy ratio and is intended to explore the chemical space of large molecular systems and solids.

show abstract

Section: Introductionmentioning

confidence: 99%

A Robust Non-Self-Consistent Tight-Binding Quantum Chemistry Method for large Molecules

Pracht

Caldeweyher²,

Ehlert³

et al. 2019

Preprint

106

View full text Add to dashboard Cite

show abstract

“…Its main concern unlike the papers mentioned above, was for systems of technological importance and for biological structures. 12,13,21 These, and other molecular electronic devices, however, will probably be replaced by robust crystalline extended devices. Such switches have been found among those that react to the chemical environment or light.…”

mentioning

confidence: 99%

Switching properties of Li–benzene complexes in a uniform electric field: a case where a “small” change makes a big difference

Sadlej-Sosnowska

2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

The effect of a homogeneous static electric field on the Li-benzene complex in two configurations, one with a larger Li-C6H6 distance ("loose") and one with a shorter distance ("tight"), has been investigated. The electric field has the same orientation as the direction of the dipole moments of the complexes. When the direction of the field intensity vector was the same as that of the dipole moment vector, optimization of the complex's geometry in one configuration resulted in switching it to the other one. Reversing the direction of the field then transformed the other configuration back to the original one. This switching behavior was observed beginning with the loose configuration and with the tight configuration. The geometrical and electronic parameters of the complex after four steps of the reversible switching have been calculated for a selected field intensity of 0.005 atomic units (a.u.), that is 0.257 V Å(-1).

show abstract

“…[31][32][33][34][35][36][37][38] Combining results of the static and dynamic studies on the switching properties of the SA molecule exposed to an external electric field, we formulate the following conclusions: Having a direct look on the trajectories calculated in dynamic simulations, we found that for low electric field values (E = 0.01 a.u.…”

Section: Figurementioning

confidence: 77%

Electric field control of proton-transfer molecular switching: molecular dynamics study on salicylidene aniline

Jankowska

Sadlej

Sobolewski

2015

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

In this letter, we propose a novel, ultrafast, efficient molecular switch whose switching mechanism involves the electric field-driven intramolecular proton transfer. By means of ab initio quantum chemical calculations and on-the-fly dynamics simulations, we examine the switching performance of an isolated salicylidene aniline molecule and analyze the perspectives of its possible use as an electric field-controlled molecular electronics unit.

show abstract

Photoswitching of Salicylidene Methylamine: A Theoretical Photodynamics Study

Cited by 42 publications

References 62 publications

A Robust Non-Self-Consistent Tight-Binding Quantum Chemistry Method for large Molecules

A Robust Non-Self-Consistent Tight-Binding Quantum Chemistry Method for large Molecules

Switching properties of Li–benzene complexes in a uniform electric field: a case where a “small” change makes a big difference

Electric field control of proton-transfer molecular switching: molecular dynamics study on salicylidene aniline

Contact Info

Product

Resources

About