Fourier transformation of the real-time trace of sub-5 fs pump-induced molecular vibration in quinoidal thiophene in solution revealed coupled modes to the electronic excitation at 206, 447, and 1466 cm(-1). Spectrogram analysis of 1466 cm(-1) (C=C stretching) mode showed that the amplitude and frequency of the mode are modulated with another low-frequency mode at about 220 cm(-1), which is down chirped being induced by the coupling with modes of even lower frequency, resulting in the irreversible relaxation due to high mode density in the low-frequency range. This Letter thus reports on observation of the modulation of vibrational frequency with a chirped frequency. (c) 2006 Elsevier B.V. All rights reserved.