Symmetry breaking in cationic polymethine dyes, part 1: Ground state potential energy surfaces and solvent effects on electronic spectra of streptocyanines

Abstract Thermally driven chemistry as well as materials’ functionality are determined by the potential energy surface of a systems electronic ground state. This makes the potential energy surface a central and powerful concept in physics, chemistry and materials science. However, direct experimental access to the potential energy surface locally around atomic centers and to its long-range structure are lacking. Here we demonstrate how sub-natural linewidth resonant inelastic soft x-ray scattering at vibrational resolution is utilized to determine ground state potential energy surfaces locally and detect long-range changes of the potentials that are driven by local modifications. We show how the general concept is applicable not only to small isolated molecules such as O2 but also to strongly interacting systems such as the hydrogen bond network in liquid water. The weak perturbation to the potential energy surface through hydrogen bonding is observed as a trend towards softening of the ground state potential around the coordinating atom. The instrumental developments in high resolution resonant inelastic soft x-ray scattering are currently accelerating and will enable broad application of the presented approach. With this multidimensional potential energy surfaces that characterize collective phenomena such as (bio)molecular function or high-temperature superconductivity will become accessible in near future.

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Theoretical insight into the C–H and C–C scission mechanism of ethane on a tetrahedral Pt4subnanocluster

RSC Advances ◽

10.1039/c5ra06550j ◽

2015 ◽

Vol 5 (51) ◽

pp. 40978-40988 ◽

Cited By ~ 2

Author(s):

Hong-Quan Fu ◽

Ben-Fang Su ◽

Hua-Qing Yang ◽

Chang-Wei Hu

Keyword(s):

Excited State ◽

Potential Energy ◽

Ground State ◽

Potential Energy Surfaces ◽

Activation Mechanism ◽

First Excited State ◽

State Potential ◽

Energy Surfaces ◽

Theoretical Insight ◽

Insight Into

The activation mechanism of C2H6on a Pt4cluster has been theoretically investigated in the ground state and the first excited state potential energy surfaces at the BPW91/Lanl2tz, aug-cc-pvtz//BPW91/Lanl2tz, 6-311++G(d, p) level.

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Ground state potential energy surfaces and bound states of M–He dimers (M=Cu,Ag,Au): A theoretical investigation

The Journal of Chemical Physics ◽

10.1063/1.3020706 ◽

2008 ◽

Vol 129 (20) ◽

pp. 204307 ◽

Cited By ~ 26

Author(s):

Fausto Cargnoni ◽

Tomasz Kuś ◽

Massimo Mella ◽

Rodney J. Bartlett

Keyword(s):

Potential Energy ◽

Theoretical Investigation ◽

Ground State ◽

Potential Energy Surfaces ◽

Bound States ◽

State Potential ◽

Energy Surfaces

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A ground state potential energy surface for HONO based on a neural network with exponential fitting functions

Physical Chemistry Chemical Physics ◽

10.1039/c7cp04010e ◽

2017 ◽

Vol 19 (33) ◽

pp. 22272-22281 ◽

Cited By ~ 19

Author(s):

Ekadashi Pradhan ◽

Alex Brown

Keyword(s):

Neural Network ◽

Potential Energy ◽

Ground State ◽

Potential Energy Surfaces ◽

Energy Surface ◽

Exponential Fitting ◽

Sum Of Products ◽

State Potential ◽

Vibrational Energies ◽

Energy Surfaces

Using CCSD(T)-F12/cc-pVTZ-F12 and CCSD(T)/CBS ab initio energies, two different six-dimensional ground state potential energy surfaces for HONO have been fit in sum-of-products form using neural network exponential fitting functions and tested by computing vibrational energies with MCTDH.

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