Abstract
Ultrafast two dimensional infrared (2D-IR) vibrational echo spectroscopy has emerged as a powerful method for the study of molecular dynamics under thermal equilibrium conditions occuring on ultrafast time scales. Here, we describe experimental details of 2D-IR vibrational echo spectroscopy including the experimental setup, pulse sequence, heterodyne detection, and extraction of the mainly absorptive part of the 2D-IR spectrum. As an experimental example, the measurements of the hydrogen bond dynamics of neat water and water in a high concentration of NaBr solution are presented and compared. The experiments are performed on OD stretching vibration of dilute HOD in H2O to eliminate contributions from vibrational excitation transport. A new experimental observable for extracting dynamical information the yields the frequency-frequency correlation function is presented. The observable is the inverse of the center line slope (CLS) of the 2D spectrum, which varies from a maximum of 1 to 0 as spectral diffusion proceeds. The CLS is the inverse of the slope of the line that connects the maxima of the peaks of a series of cuts through the 2D spectrum that are parallel to the frequency axis associated with the first radiation field-matter interaction. Comparisons of the dynamics obtained from the data on water and the concentrated NaBr solutions show that the hydrogen bond dynamics of water around ions are much slower than in bulk water.
| Original language | English |
|---|---|
| Pages (from-to) | 704-718 |
| Number of pages | 15 |
| Journal | Laser Physics Letters |
| Volume | 4 |
| Issue number | 10 |
| DOIs | |
| Publication status | Published - 2007 Oct 1 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Physics and Astronomy (miscellaneous)
- Instrumentation
Cite this
Ultrafast 2D-IR vibrational echo spectroscopy : A probe of molecular dynamics. / Park, Sungnam; Kwak, Kyungwon; Fayer, M. D.
In: Laser Physics Letters, Vol. 4, No. 10, 01.10.2007, p. 704-718.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Ultrafast 2D-IR vibrational echo spectroscopy
T2 - A probe of molecular dynamics
AU - Park, Sungnam
AU - Kwak, Kyungwon
AU - Fayer, M. D.
PY - 2007/10/1
Y1 - 2007/10/1
N2 - Ultrafast two dimensional infrared (2D-IR) vibrational echo spectroscopy has emerged as a powerful method for the study of molecular dynamics under thermal equilibrium conditions occuring on ultrafast time scales. Here, we describe experimental details of 2D-IR vibrational echo spectroscopy including the experimental setup, pulse sequence, heterodyne detection, and extraction of the mainly absorptive part of the 2D-IR spectrum. As an experimental example, the measurements of the hydrogen bond dynamics of neat water and water in a high concentration of NaBr solution are presented and compared. The experiments are performed on OD stretching vibration of dilute HOD in H2O to eliminate contributions from vibrational excitation transport. A new experimental observable for extracting dynamical information the yields the frequency-frequency correlation function is presented. The observable is the inverse of the center line slope (CLS) of the 2D spectrum, which varies from a maximum of 1 to 0 as spectral diffusion proceeds. The CLS is the inverse of the slope of the line that connects the maxima of the peaks of a series of cuts through the 2D spectrum that are parallel to the frequency axis associated with the first radiation field-matter interaction. Comparisons of the dynamics obtained from the data on water and the concentrated NaBr solutions show that the hydrogen bond dynamics of water around ions are much slower than in bulk water.
AB - Ultrafast two dimensional infrared (2D-IR) vibrational echo spectroscopy has emerged as a powerful method for the study of molecular dynamics under thermal equilibrium conditions occuring on ultrafast time scales. Here, we describe experimental details of 2D-IR vibrational echo spectroscopy including the experimental setup, pulse sequence, heterodyne detection, and extraction of the mainly absorptive part of the 2D-IR spectrum. As an experimental example, the measurements of the hydrogen bond dynamics of neat water and water in a high concentration of NaBr solution are presented and compared. The experiments are performed on OD stretching vibration of dilute HOD in H2O to eliminate contributions from vibrational excitation transport. A new experimental observable for extracting dynamical information the yields the frequency-frequency correlation function is presented. The observable is the inverse of the center line slope (CLS) of the 2D spectrum, which varies from a maximum of 1 to 0 as spectral diffusion proceeds. The CLS is the inverse of the slope of the line that connects the maxima of the peaks of a series of cuts through the 2D spectrum that are parallel to the frequency axis associated with the first radiation field-matter interaction. Comparisons of the dynamics obtained from the data on water and the concentrated NaBr solutions show that the hydrogen bond dynamics of water around ions are much slower than in bulk water.
KW - Frequency-frequency correlation function
KW - Heterodyne detection
KW - Hydrogen bond
KW - Spectral diffusion
KW - Third-order four wave mixing
KW - Two dimensional infrared vibrational echo spectroscopy
UR - http://www.scopus.com/inward/record.url?scp=34848915033&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=34848915033&partnerID=8YFLogxK
U2 - 10.1002/lapl.200710046
DO - 10.1002/lapl.200710046
M3 - Article
AN - SCOPUS:34848915033
VL - 4
SP - 704
EP - 718
JO - Laser Physics Letters
JF - Laser Physics Letters
SN - 1612-2011
IS - 10
ER -