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Azide–water intermolecular coupling measured by two-color two-dimensional infrared spectroscopy
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View: Figures


Image of FIG. 1.
FIG. 1.

Linear spectrum of 1 M solution in D2O (black line). The asymmetric stretch vibration is found at 2044 cm−1 and the OD-stretch band is a wide, asymmetric peak with a maximum at ∼2510 cm−1 (blue dashed line). The OD-stretch band of pure D2O (green line) is shown for comparison.

Image of FIG. 2.
FIG. 2.

Two-color 2D-IR spectra of in D2O at population times t2 = 300, 400, and 1200 fs. Initially, a rather narrow and weak bleach/stimulated emission signal is observed (blue band), whose frequency coincides with the maximum of the linear absorption spectrum (blue dashed line, as in Fig. 1). Furthermore, a much broader excited state absorption signals is observed (red band). The bleach contribution grows in time, while the excited state absorption peak decays. After ∼1 ps, thermalization dominates in the form of a strong and wide bleach contribution.

Image of FIG. 3.
FIG. 3.

Cuts of 2D-IR spectra at t2 = 400 fs along ω pump = 2048 cm−1 comparing 2D-IR signal sizes for in D2O with in H2O. Since no 2D-IR response in H2O is observed, the measured signal in D2O originates from an intermolecular cross-peak.

Image of FIG. 4.
FIG. 4.

Time dependence of the intensity of the peak of the 1–2 excited state absorption signal. The data are fit by Eq. (4), revealing the two time constants τ1 = 150 fs and τ2=1.7 ps.

Image of FIG. 5.
FIG. 5.

Vibrational level scheme for coupled oscillators and the possible origins of 2D-IR cross-peaks. The symmetric stretch of and OD-stretch are coupled and share a common ground state. The pump pulse induces a transition into the first excited state of the asymmetric stretch vibration of . In the direct coupling case, the probe pulse moves the excitation up to the |11⟩ state. In the case of population transfer, the oscillation moves from the |10⟩ to the |01⟩ state and the probe pulse induces further absorption into the |02⟩ state.

Image of FIG. 6.
FIG. 6.

Linear spectra of saturated KSeCN (black line) and KSe13CN (red line) solutions in D2O. CN-stretches are observed at 2070 and 2020 cm−1 for KSeCN and KSe13CN, respectively. The OD-stretch band is split into two peaks, with the shape and intensities being almost identical for both salts. In a KSeCN and KSe13CN solution in H2O, two combination bands of the ion are visible – one between the CN-stretch and the SeCN bend and the other between the CN- and SeC-stretches (green line for KSeCN, blue line for KSe13CN, both upscaled by ∼×50).

Image of FIG. 7.
FIG. 7.

KSeCN and KSe13CN in D2O. (a) Linear spectra of the OD-stretch in KSeCN solutions in D2O and the combination bands of KSeCN (green line) and KSe13CN (blue line) (b) 2D-IR spectrum of KSe13CN in D2O at population time t 2=400 fs, (c) 2D-IR spectrum of KSeCN in D2O at t 2 = 400 fs. Upon 13C labeling, the 2D-IR cross-peaks shift not only in the pump frequency, ω pump , but also in the probe frequency, ω probe .


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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Azide–water intermolecular coupling measured by two-color two-dimensional infrared spectroscopy