Dissecting the THz spectrum of liquid water from first principles via correlations in time and space

被引:388
作者
Heyden, Matthias [1 ]
Sun, Jian [2 ]
Funkner, Stefan [1 ]
Mathias, Gerald [2 ]
Forbert, Harald [2 ]
Havenith, Martina [1 ]
Marx, Dominik [2 ]
机构
[1] Ruhr Univ Bochum, Lehrstuhl Phys Chem 2, D-44780 Bochum, Germany
[2] Ruhr Univ Bochum, Lehrstuhl Theoret Chem, D-44780 Bochum, Germany
关键词
ab initio molecular dynamics; hydrogen-bonding; solvation; infrared spectroscopy; vibrational modes; RAMAN-SPECTRA; OPTICAL-CONSTANTS; INFRARED-SPECTRUM; BOND NETWORK; DYNAMICS; PROTEIN; MOLECULES; FLUCTUATIONS; SPECTROSCOPY; SIMULATIONS;
D O I
10.1073/pnas.0914885107
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
Solvation of molecules in water is at the heart of a myriad of molecular phenomena and of crucial importance to understanding such diverse issues as chemical reactivity or biomolecular function. Complementing well-established approaches, it has been shown that laser spectroscopy in the THz frequency domain offers new insights into hydration from small solutes to proteins. Upon introducing spatially-resolved analyses of the absorption cross section by simulations, the sensitivity of THz spectroscopy is traced back to characteristic distance-dependent modulations of absorption intensities for bulk water. The prominent peak at approximate to 200 cm(-1) is dominated by first-shell dynamics, whereas a concerted motion involving the second solvation shell contributes most significantly to the absorption at about 80 cm(-1) approximate to 2.4 THz. The latter can be understood in terms of an umbrella-like motion of two hydrogen-bonded tetrahedra along the connecting hydrogen bond axis. Thus, a modification of the hydrogen bond network, e. g., due to the presence of a solute, is expected to affect vibrational motion and THz absorption intensity at least on a length scale that corresponds to two layers of solvating water molecules. This result provides a molecular mechanism explaining the experimentally determined sensitivity of absorption changes in the THz domain in terms of distinct, solute-induced dynamical properties in solvation shells of (bio)molecules-even in the absence of well-defined resonances.
引用
收藏
页码:12068 / 12073
页数:6
相关论文
共 44 条
[1]   IR and Raman spectra of liquid water: Theory and interpretation [J].
Auer, B. M. ;
Skinner, J. L. .
JOURNAL OF CHEMICAL PHYSICS, 2008, 128 (22)
[2]   Water as an active constituent in cell biology [J].
Ball, Philip .
CHEMICAL REVIEWS, 2008, 108 (01) :74-108
[3]   Infrared intensities of liquids .20. The intensity of the OH stretching band of liquid water revisited, and the best current values of the optical constants of H2O(1) at 25 degrees C between 15,000 and 1 cm(-1) [J].
Bertie, JE ;
Lan, ZD .
APPLIED SPECTROSCOPY, 1996, 50 (08) :1047-1057
[4]   Opinion - Do we underestimate the importance of water in cell biology? [J].
Chaplin, Martin .
NATURE REVIEWS MOLECULAR CELL BIOLOGY, 2006, 7 (11) :861-866
[5]   EVIDENCE OF QUANTUM CORRELATION-EFFECTS OF PROTONS AND DEUTERONS IN THE RAMAN-SPECTRA OF LIQUID H2O-D2O [J].
CHATZIDIMITRIOUDREISMANN, CA ;
KRIEGER, UK ;
MOLLER, A ;
STERN, M .
PHYSICAL REVIEW LETTERS, 1995, 75 (16) :3008-3011
[6]   Role of dipolar correlations in the infrared spectra of water and ice [J].
Chen, Wei ;
Sharma, Manu ;
Resta, Raffaele ;
Galli, Giulia ;
Car, Roberto .
PHYSICAL REVIEW B, 2008, 77 (24)
[7]   Protein folding mediated by solvation:: Water expulsion and formation of the hydrophobic core occur after the structural collapse [J].
Cheung, MS ;
García, AE ;
Onuchic, JN .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2002, 99 (02) :685-690
[8]   An extended dynamical hydration shell around proteins [J].
Ebbinghaus, Simon ;
Kim, Seung Joong ;
Heyden, Matthias ;
Yu, Xin ;
Heugen, Udo ;
Gruebele, Martin ;
Leitner, David M. ;
Havenith, Martina .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2007, 104 (52) :20749-20752
[9]   Development of transferable interaction potentials for water. V. Extension of the flexible, polarizable, Thole-type model potential (TTM3-F, v. 3.0) to describe the vibrational spectra of water clusters and liquid water [J].
Fanourgakis, George S. ;
Xantheas, Sotiris S. .
JOURNAL OF CHEMICAL PHYSICS, 2008, 128 (07)
[10]   Slaving: Solvent fluctuations dominate protein dynamics and functions [J].
Fenimore, PW ;
Frauenfelder, H ;
McMahon, BH ;
Parak, FG .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2002, 99 (25) :16047-16051