scholarly journals Nonlinear spectroscopy in the condensed phase: The role of Duschinsky rotations and third order cumulant contributions

2020 ◽  
Vol 153 (4) ◽  
pp. 044127 ◽  
Author(s):  
Tim J. Zuehlsdorff ◽  
Hanbo Hong ◽  
Liang Shi ◽  
Christine M. Isborn
Keyword(s):  
Condensed Phase ◽  
Nonlinear Spectroscopy ◽  
Third Order

scholarly journals Nonlinear Spectroscopy in the Condensed Phase: The Role of Duschinsky Rotations and Third Order Cumulant Contributions

2020 ◽  
Author(s):  
Tim Zuehlsdorff ◽  
Hanbo Hong ◽  
Liang Shi ◽  
Christine Isborn
Keyword(s):  
Excited State ◽  
Condensed Phase ◽  
Nonlinear Optical ◽  
Order Term ◽  
Optical Spectra ◽  
Cumulant Expansion ◽  
Third Order ◽  
The Third ◽  
Mode Mixing

First-principles modeling of nonlinear optical spectra in the condensed phase is highly challenging because both environment and vibronic interactions can play a large role in determining spectral shapes and excited state dynamics. Here, we compute two dimensional electronic spectroscopy (2DES) signals based on a cumulant expansion of the energy gap fluctuation operator, with a specific focus on analyzing mode mixing effects introduced by the Duschinsky rotation and the role of the third order term in the cumulant expansion for both model and realistic condensed phase systems. We show that for a harmonic model system, the third order cumulant correction captures effects introduced by a mismatch in curvatures of ground and excited state potential energy surfaces, as well as effects of mode mixing. We also demonstrate that 2DES signals can be accurately reconstructed from purely classical correlation functions using quantum correction factors. We then compute nonlinear optical spectra for the Nile red and Methylene blue chromophores in solution, assessing the third order cumulant contribution for realistic systems. We show that the third order cumulant correction is strongly dependent on the treatment of the solvent environment, revealing the interplay between environmental polarization and the electronic-vibrational coupling.

scholarly journals Nonlinear Spectroscopy in the Condensed Phase: The Role of Duschinsky Rotations and Third Order Cumulant Contributions

2020 ◽  
Author(s):  
Tim Zuehlsdorff ◽  
Hanbo Hong ◽  
Liang Shi ◽  
Christine Isborn
Keyword(s):  
Excited State ◽  
Condensed Phase ◽  
Nonlinear Optical ◽  
Order Term ◽  
Optical Spectra ◽  
Cumulant Expansion ◽  
Third Order ◽  
The Third ◽  
Mode Mixing

First-principles modeling of nonlinear optical spectra in the condensed phase is highly challenging because both environment and vibronic interactions can play a large role in determining spectral shapes and excited state dynamics. Here, we compute two dimensional electronic spectroscopy (2DES) signals based on a cumulant expansion of the energy gap fluctuation operator, with a specific focus on analyzing mode mixing effects introduced by the Duschinsky rotation and the role of the third order term in the cumulant expansion for both model and realistic condensed phase systems. We show that for a harmonic model system, the third order cumulant correction captures effects introduced by a mismatch in curvatures of ground and excited state potential energy surfaces, as well as effects of mode mixing. We also demonstrate that 2DES signals can be accurately reconstructed from purely classical correlation functions using quantum correction factors. We then compute nonlinear optical spectra for the Nile red and Methylene blue chromophores in solution, assessing the third order cumulant contribution for realistic systems. We show that the third order cumulant correction is strongly dependent on the treatment of the solvent environment, revealing the interplay between environmental polarization and the electronic-vibrational coupling.

scholarly journals A Unified Mathematical Formalism for First to Third Order Dielectric Response of Matter: Application to Surface-Specific Two-Colour Vibrational Optical Spectroscopy

Symmetry ◽  
2021 ◽  
Vol 13 (1) ◽  
pp. 153 ◽  
Author(s):  
Christophe Humbert ◽  
Thomas Noblet
Keyword(s):  
Dielectric Response ◽  
Structure And Properties ◽  
Linear Optics ◽  
Third Order ◽  
Mathematical Functions ◽  
Sum Frequency ◽  
Non Linear Optics ◽  
Non Linear ◽  
Light Excitation

To take advantage of the singular properties of matter, as well as to characterize it, we need to interact with it. The role of optical spectroscopies is to enable us to demonstrate the existence of physical objects by observing their response to light excitation. The ability of spectroscopy to reveal the structure and properties of matter then relies on mathematical functions called optical (or dielectric) response functions. Technically, these are tensor Green’s functions, and not scalar functions. The complexity of this tensor formalism sometimes leads to confusion within some articles and books. Here, we do clarify this formalism by introducing the physical foundations of linear and non-linear spectroscopies as simple and rigorous as possible. We dwell on both the mathematical and experimental aspects, examining extinction, infrared, Raman and sum-frequency generation spectroscopies. In this review, we thus give a personal presentation with the aim of offering the reader a coherent vision of linear and non-linear optics, and to remove the ambiguities that we have encountered in reference books and articles.

scholarly journals Protein crystal lattices are dynamic assemblies: the role of conformational entropy in the protein condensed phase

IUCrJ ◽  
2018 ◽  
Vol 5 (2) ◽  
pp. 130-140 ◽  
Author(s):  
Margarita Dimova ◽  
Yancho D. Devedjiev
Keyword(s):  
Condensed Phase ◽  
Protein Structures ◽  
Van Der Waals Interactions ◽  
Protein Crystal ◽  
Crystal Formation ◽  
Conformational Entropy ◽  
Crystal Lattices ◽  
Crystal Contacts ◽  
First Time

Until recently, the occurrence of conformational entropy in protein crystal contacts was considered to be a very unlikely event. A study based on the most accurately refined protein structures demonstrated that side-chain conformational entropy and static disorder might be common in protein crystal lattices. The present investigation uses structures refined using ensemble refinement to show that although paradoxical, conformational entropy is likely to be the major factor in the emergence and integrity of the protein condensed phase. This study reveals that the role of shape entropy and local entropic forces expands beyond the onset of crystallization. For the first time, the complete pattern of intermolecular interactions by protein atoms in crystal lattices is presented, which shows that van der Waals interactions dominate in crystal formation.

scholarly journals Nested Recharge Systems in Mountain Block Hydrology: High-Elevation Snowpack Generates Low-Elevation Overwinter Baseflow in a Rocky Mountain River

Water ◽  
2021 ◽  
Vol 13 (16) ◽  
pp. 2249
Author(s):  
Éowyn M. S. Campbell ◽  
M. Cathryn Ryan
Keyword(s):  
Rocky Mountain ◽  
High Elevation ◽  
Third Order ◽  
Relative Temperature ◽  
Local Flow ◽  
Fracture Systems ◽  
Lower Elevation ◽  
Flow Systems ◽  
Longitudinal Sampling

The majority of each year′s overwinter baseflow (i.e., winter streamflow) in a third-order eastern slopes tributary is generated from annual melting of high-elevation snowpack which is transmitted through carbonate and siliciclastic aquifers. The Little Elbow River and its tributaries drain a bedrock system formed by repeated thrust faults that express as the same siliciclastic and carbonate aquifers in repeating outcrops. Longitudinal sampling over an 18 km reach was conducted at the beginning of the overwinter baseflow season to assess streamflow provenance. Baseflow contributions from each of the two primary aquifer types were apportioned using sulfate, δ34SSO4, and silica concentrations, while δ18OH2O composition was used to evaluate relative temperature and/or elevation of the original precipitation. Baseflow in the upper reaches of the Little Elbow was generated from lower-elevation and/or warmer precipitation primarily stored in siliciclastic units. Counterintuitively, baseflow generated in the lower-elevation reaches originated from higher-elevation and/or colder precipitation stored in carbonate units. These findings illustrate the role of nested flow systems in mountain block recharge: higher-elevation snowmelt infiltrates through fracture systems in the cliff-forming—often higher-elevation—carbonates, moving to the lower-elevation valley through intermediate flow systems, while winter baseflow in local flow systems in the siliciclastic valleys reflects more influence from warmer precipitation. The relatively fast climatic warming of higher elevations may alter snowmelt timing, leaving winter water supply vulnerable to climatic change.

Collective many-body resonances in condensed phase nonlinear spectroscopy

2002 ◽  
Vol 116 (12) ◽  
pp. 5007 ◽  
Author(s):  
Andreas Tortschanoff ◽  
Shaul Mukamel
Keyword(s):  
Condensed Phase ◽  
Nonlinear Spectroscopy ◽  
Many Body

Third-Order Nonlinear Spectroscopy of Coupled Vibrations

2002 ◽  
pp. 169-181 ◽  
Author(s):  
O. Golonzka ◽  
M. Khalil ◽  
N. Demirdöven ◽  
A. Tokmakoff
Keyword(s):  
Nonlinear Spectroscopy ◽  
Third Order ◽  
Coupled Vibrations

Functional heterogeneity of endothelial P2 purinoceptors in the cerebrovascular tree of the rat

1999 ◽  
Vol 277 (3) ◽  
pp. H893-H900 ◽  
Author(s):  
Junping You ◽  
T. David Johnson ◽  
Sean P. Marrelli ◽  
Robert M. Bryan
Keyword(s):  
Cerebral Arteries ◽  
No Synthase ◽  
Third Order ◽  
Selective Agonist ◽  
Middle Cerebral Arteries ◽  
Spontaneous Tone ◽  
A Minor ◽  
Calcium Activated Potassium Channel ◽  
Dose Dependent

The effects of stimulating P2Y1 or P2Y2 purinoceptors on the endothelium of isolated middle cerebral arteries (MCAs), third-order branches of the MCA (bMCAs), and penetrating arterioles (PAs) of the rat were studied. After pressurization and development of spontaneous tone (25% contraction), resting diameters for MCAs, bMCAs, and PAs were 203 ± 5 ( n = 50), 99 ± 2 ( n = 42), and 87 ± 2 μm ( n = 53), respectively. Luminal application of the P2Y1-selective agonist 2-methylthioadenosine 5′-triphosphate elicited dose-dependent dilations (or loss of intrinsic tone) in MCAs but not in bMCAs or PAs. The dilation in MCAs was completely blocked by removal of the endothelium or by nitro-l-arginine methyl ester (10−5 M), an inhibitor of NO synthase. Luminal application of the P2Y2-selective agonist ATP elicited dilations in MCAs, bMCAs, and PAs. Removal of the endothelium abolished the dilations in all vessel groups. Dilations in MCAs have been shown to involve both NO and endothelium-derived hyperpolarizing factor (EDHF). The dilations in bMCAs and PAs had a minor NO component and prominent EDHF component; that is, 1) the dilations to ATP were not diminished by the combined inhibition of NO synthase and cyclooxygenase, 2) the dilations were accompanied by significant hyperpolarizations of the vascular smooth muscle (∼15 mV), and 3) the dilations were completely abolished by the calcium-activated potassium channel blocker charybdotoxin. We concluded that the role of NO in purinoceptor-induced dilations diminishes along the cerebrovascular tree in the rat, whereas the role of EDHF becomes more prominent.

Effects of hydrogen peroxide on the responsiveness of isolated canine bronchi: role of prostaglandin E2 and I2

1992 ◽  
Vol 263 (3) ◽  
pp. L402-L408 ◽  
Author(s):  
Y. Gao ◽  
P. M. Vanhoutte
Keyword(s):  
Hydrogen Peroxide ◽  
Methylene Blue ◽  
Smooth Muscle ◽  
Prostaglandin E2 ◽  
Respiratory Epithelium ◽  
Isometric Tension ◽  
Third Order ◽  
Bronchial Smooth Muscle ◽  
Cyclic Monophosphate

The present study was design to determine the role of prostaglandin E2 and I2 in the responses of isolated canine airways to H2O2. Rings of canine third-order bronchi, some of which had undergone mechanical denudation of the epithelium, were suspended in organ chambers; isometric tension was recorded. During contractions to acetylcholine, H2O2 induced concentration-dependent relaxations. The relaxations were attenuated significantly by indomethacin, acetylsalicylic acid, and methylene blue. H2O2 increased the release of prostaglandin E2 and 6-keto-prostaglandin F1 alpha and the content of adenosine 3',5'-cyclic monophosphate (cAMP). These effects were abolished by indomethacin or methylene blue. H2O2 did not affect the content of guanosine 3',5'-cyclic monophosphate significantly. These observations suggest that 1) H2O2 relaxes canine bronchial smooth muscle and 2) elevation of tissue content of cAMP induced by prostaglandin E2 and I2 may be involved. These phenomena did not appear to be modulated by the respiratory epithelium, since H2O2-induced relaxations and increases in the release of PGE2 and 6-ketoprostaglandin F1 alpha were similar in preparations with and without epithelium. However, after treatment with methylene blue, H2O2 induced contractions only in preparations with epithelium. These epithelium-dependent contractions were not affected by inhibitors of cyclooxygenase and lipoxygenase.

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