Vacuum ultraviolet spectroscopy of the lowest-lying electronic state in subcritical and supercritical water

Nature Communications
Timothy W MarinDaniel M Chipman

Abstract

The nature and extent of hydrogen bonding in water has been scrutinized for decades, including how it manifests in optical properties. Here we report vacuum ultraviolet absorption spectra for the lowest-lying electronic state of subcritical and supercritical water. For subcritical water, the spectrum redshifts considerably with increasing temperature, demonstrating the gradual breakdown of the hydrogen-bond network. Tuning the density at 381 °C gives insight into the extent of hydrogen bonding in supercritical water. The known gas-phase spectrum, including its vibronic structure, is duplicated in the low-density limit. With increasing density, the spectrum blueshifts and the vibronic structure is quenched as the water monomer becomes electronically perturbed. Fits to the supercritical water spectra demonstrate consistency with dimer/trimer fractions calculated from the water virial equation of state and equilibrium constants. Using the known water dimer interaction potential, we estimate the critical distance between molecules (ca. 4.5 Å) needed to explain the vibronic structure quenching.

References

Jun 1, 2000·Proceedings of the National Academy of Sciences of the United States of America·H HayashiC Kao
Aug 15, 2002·Chemical Reviews·Naoko Akiya, Phillip E Savage
Jul 23, 2004·The Journal of Chemical Physics·Yoshihiro TawadaKimihiko Hirao
Feb 9, 2005·Physical Review Letters·P H HahnJ Bernholc
Mar 3, 2005·The Journal of Chemical Physics·Daniel M Chipman
Sep 27, 2006·The Journal of Chemical Physics·Timothy W MarinDavid M Bartels
Apr 28, 2007·The Journal of Chemical Physics·Jong-Won SongKimihiko Hirao
Mar 5, 2009·The Journal of Chemical Physics·Christopher G EllesStephen E Bradforth
Jul 2, 2010·The Journal of Chemical Physics·Paulo Cabral do Couto, Daniel M Chipman
Mar 3, 2011·The Journal of Chemical Physics·M Yu Tretyakov, D S Makarov
Jan 21, 2009·Journal of Physics. Condensed Matter : an Institute of Physics Journal·Viviana GarbuioOlivia Pulci
Feb 2, 2015·The Review of Scientific Instruments·Ireneusz Janik, Timothy W Marin
Feb 18, 2015·The Journal of Physical Chemistry. a·Piotr JankowskiKrzysztof Szalewicz
Dec 9, 2015·Nature Communications·Anders Nilsson, Lars G M Pettersson
Jun 1, 2016·Chemical Reviews·Thomas FranssonAnders Nilsson

❮ Previous
Next ❯

Citations

Sep 15, 2018·Physical Chemistry Chemical Physics : PCCP·Laura Zanetti-PolziAndrea Amadei
Sep 24, 2020·Physical Chemistry Chemical Physics : PCCP·Jiangbo Tim ZhaoMarkus A Schmidt
Oct 31, 2019·Physical Chemistry Chemical Physics : PCCP·Timothy W MarinDavid M Bartels
Mar 13, 2021·Physical Chemistry Chemical Physics : PCCP·Sebastian MalerzStephan Thürmer
Jun 15, 2021·Photochemistry and Photobiology·Joseph RabaniJames R Bolton
Jun 15, 2019·The Journal of Physical Chemistry. a·Dhritiman BhattacharyyaStephen E Bradforth
Oct 29, 2021·Chemical Communications : Chem Comm·Pan LuoFangjun Wang

❮ Previous
Next ❯

Methods Mentioned

BETA
X-ray

Software Mentioned

EOM
Igor Pro
Chem
CCSD

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.

Related Papers

Journal of Molecular Spectroscopy
J M FernándezS Montero
Physical Chemistry Chemical Physics : PCCP
Flaviu S CipciganGlenn J Martyna
Angewandte Chemie
Andrea Kruse, Eckhard Dinjus
© 2022 Meta ULC. All rights reserved