FOM Institute AMOLF, Science Park 104, 1098 XG Amsterdam, The Netherlands.
J Phys Chem A. 2010 Oct 7;114(39):10523-30. doi: 10.1021/jp105506a.
We study the rate and mechanism of deuteron transfer from the photoacids 1-naphtol-4-sulfonate (1-NPS) and 2-naphtol-3,7-disulphonate (2-NPS) to acetate base in aqueous (D(2)O) solution. The photoacids are activated by excitation with 100 fs laser pulses at 267 nm. The electronic absorption and stimulated emission spectra of the photoacid and the conjugate photobase and the vibrational absorption spectra of the hydrated deuteron and the acetate base are probed with broad-band delayed 100 fs pulses at visible and mid-infrared wavelengths, respectively. A significant fraction of the deuteron transfer events are observed to occur on a timescale of <1 ps within hydrogen-bonded contact photoacid-acetate complexes. For 1-NPS, this fraction is much higher than for 2-NPS. At later delay times, the reaction is dominated by deuteron transfer through short-living water wires of different lengths that connect the photoacid and the acetate base.
我们研究了氘从 1-萘酚-4-磺酸盐（1-NPS）和 2-萘酚-3,7-二磺酸盐（2-NPS）转移到水相（D（2）O）溶液中醋酸盐的速率和机制。光酸通过在 267nm 处用 100fs 激光脉冲激发而被激活。用宽带延迟 100fs 可见光和中红外波长的脉冲分别探测光酸和共轭光碱的电子吸收和受激发射光谱以及水合氘和醋酸盐的振动吸收光谱。在氢键连接的光酸-醋酸盐复合物中，观察到相当一部分氘转移事件在<1ps 的时间尺度内发生。对于 1-NPS，这个分数比 2-NPS 高得多。在稍后的延迟时间内，反应主要由通过连接光酸和醋酸盐的不同长度的短寿命水线进行的氘转移主导。
