Extreme cross-peak 2D spectroscopy

Scholes, Gregory D.

doi:10.1073/pnas.1410105111

Cited by 4 publications

(3 citation statements)

References 20 publications

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“…Two-dimensional electronic spectroscopy (2DES) is [1][2][3][4][5][6][7][8][9][10] steadily becoming a favorable tool to track photoinduced phenomena in complex systems. [1][2][3][4][5][6][7][8][9][10][11] This is due to its enhanced spatial resolution as compared to its one-dimensional pump-probe (1D-PP) counterpart, stemming from the use of an extra laser pulse in the build-up of the third-order nonlinear response signal compared to the latter: a typical experiment is performed by scanning time delays between the first and second laser pulses (t 1 ) for a given time delay between the second and third pulses (t 2 ), which can be considered as the analogue of the waiting time between pump and probe pulses in PP spectroscopy, and between a third pulse and a local oscillator (t 3 ), which heterodynes the field emitted by the sample in response to the perturbation by the three incident pulses. By Fourier transforming the signal along t 1 and t 3 , 2D frequency maps with signals S(Ω 1 ,t 2 ,Ω 3 ) can be obtained at different waiting times t 2 , where all electronic transitions involved in the three field-matter interactions are recorded [12][13][14].…”

Section: Introductionmentioning

confidence: 99%

The highly excited-state manifold of guanine: calibration for nonlinear electronic spectroscopy simulations

et al. 2018

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A computational protocol based on the complete and restricted active space self-consistent field (CASSCF/RASSCF) methods and their second-order perturbation theory extensions (CASPT2/RASPT2) is employed to benchmark the highly excited state manifold of the DNA/RNA canonical purine nucleobase guanine in vacuo. Several RASPT2 schemes are tested, displaying a steady convergence of electronic transition energies and dipole moments upon active space enlargement towards the reference values. The outcome allows calibrating and optimizing computational efforts by considering cheaper and more approximate RAS schemes that could enable the characterization of the excited state manifolds of multichromophoric systems, such as DNA/RNA nulceobase dimers or multimers. Simulations of two-dimensional electronic spectra show similar trends to those observed on the other purine nucleobase adenine, deviating from this and other pyrimidine nucleobases in featuring its main excited state absorption signal, embodied by sizable double HOMO to LUMO excitation contributions, in the UV probing window.

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Section: Introductionmentioning

confidence: 99%

The highly excited-state manifold of guanine: calibration for nonlinear electronic spectroscopy simulations

et al. 2018

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“…Nonlinear optical electronic spectroscopy, through a plethora of diverse experimental variations, provides an ultimate technique to track photoinduced events, 11,12 yet yielding a vast amount of signals hard to interpret and understand. It is here where theoretical chemistry comes at hand, 13 as it allows simulating the spectra and provides a route map to recognize the distinct fingerprints and assign them to specific molecular conformations and electronic excited state transitions.…”

Section: Introductionmentioning

confidence: 99%

Modeling the high-energy electronic state manifold of adenine: Calibration for nonlinear electronic spectroscopy

Nenov

Giussani

Segarra‐Martí

et al. 2015

The Journal of Chemical Physics

102

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Pump-probe electronic spectroscopy using femtosecond laser pulses has evolved into a standard tool for tracking ultrafast excited state dynamics. Its two-dimensional (2D) counterpart is becoming an increasingly available and promising technique for resolving many of the limitations of pump-probe caused by spectral congestion. The ability to simulate pump-probe and 2D spectra from ab initio computations would allow one to link mechanistic observables like molecular motions and the making/breaking of chemical bonds to experimental observables like excited state lifetimes and quantum yields. From a theoretical standpoint, the characterization of the electronic transitions in the visible (Vis)/ultraviolet (UV), which are excited via the interaction of a molecular system with the incoming pump/probe pulses, translates into the determination of a computationally challenging number of excited states (going over 100) even for small/medium sized systems. A protocol is therefore required to evaluate the fluctuations of spectral properties like transition energies and dipole moments as a function of the computational parameters and to estimate the effect of these fluctuations on the transient spectral appearance. In the present contribution such a protocol is presented within the framework of complete and restricted active space self-consistent field theory and its second-order perturbation theory extensions. The electronic excited states of adenine have been carefully characterized through a previously presented computational recipe [Nenov et al., Comput. Theor. Chem. 1040-1041, 295-303 (2014]. A wise reduction of the level of theory has then been performed in order to obtain a computationally less demanding approach that is still able to reproduce the characteristic features of the reference data. Foreseeing the potentiality of 2D electronic spectroscopy to track polynucleotide ground and excited state dynamics, and in particular its expected ability to provide conformational dependent fingerprints in dimeric systems, the performances of the selected reduced level of calculations have been tested in the construction of 2D electronic spectra for the in vacuo adenine monomer and the unstacked adenine homodimer, thereby exciting the L b /L a transitions with the pump pulse pair and probing in the Vis to near ultraviolet spectral window. C 2015 AIP Publishing LLC. [http://dx

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“…vibrational or electronic), even if different central pump and probe wavelengths were used [ 91 , 118 ]. This changed with the advent of ‘extreme cross’ peak spectroscopies [ 119 ] such as 2D electronic–vibrational (2DEV) [ 120 ] and 2D vibrational–electronic (2DVE) [ 121 ] spectroscopies. These mixed electronic–vibrational spectroscopies are uniquely placed to investigate how the interplay and coupling between electronic and nuclear degrees of freedom dictates the non-radiative relaxation dynamics of molecules, especially those that involve conical intersections (CIs).…”

Section: Extreme Cross-peak Multidimensional Spectroscopymentioning

confidence: 99%

Recent advances in multidimensional ultrafast spectroscopy

Oliver¹

2018

R. Soc. open sci.

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Multidimensional ultrafast spectroscopies are one of the premier tools to investigate condensed phase dynamics of biological, chemical and functional nanomaterial systems. As they reach maturity, the variety of frequency domains that can be explored has vastly increased, with experimental techniques capable of correlating excitation and emission frequencies from the terahertz through to the ultraviolet. Some of the most recent innovations also include extreme cross-peak spectroscopies that directly correlate the dynamics of electronic and vibrational states. This review article summarizes the key technological advances that have permitted these recent advances, and the insights gained from new multidimensional spectroscopic probes.

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Extreme cross-peak 2D spectroscopy

Cited by 4 publications

References 20 publications

The highly excited-state manifold of guanine: calibration for nonlinear electronic spectroscopy simulations

The highly excited-state manifold of guanine: calibration for nonlinear electronic spectroscopy simulations

Modeling the high-energy electronic state manifold of adenine: Calibration for nonlinear electronic spectroscopy

Recent advances in multidimensional ultrafast spectroscopy

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