Size dependent reaction kinetics of small gold clusters with carbon monoxide: Influence of internal degrees of freedom and carbonyl complex stability

The reactions of free gold clusters Au–, % MathType!MTEF!2!1!+- % feaafaart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaeyqaiaabw % hadaqhaaWcbaGaaGOmaaqaaiabgkHiTaaaaaa!397D! $$ {\rm{Au}}_2^ - $$ , and % MathType!MTEF!2!1!+- % feaafaart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaeyqaiaabw % hadaqhaaWcbaGaaG4maaqaaiabgkHiTaaaaaa!397E! $$ {\rm{Au}}_3^ - $$ with carbon monoxide are studied in an rf-octopole ion trap experiment at cryogenic temperatures. While Au– is unreactive toward CO over the whole temperature range investigated, the two and three atom cluster anions show a maximum adsorption of two CO molecules at temperatures below 250 K. From time resolved trapping experiments the strongly cluster size dependent reaction kinetics are obtained and a distinct reaction mechanism is deduced. The size dependence of the measured rate coefficients reveals the preferred formation and particular stability of the carbonyl complex % MathType!MTEF!2!1!+- % feaafaart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaeyqaiaabw % hadaWgaaWcbaGaaG4maaqabaGccaGGOaGaae4qaiaab+eacaGGPaWa % a0baaSqaaiaaikdaaeaacqGHsislaaaaaa!3D61! $$ {\rm{Au}}_3 ({\rm{CO}})_2^ - $$ . Through RRK analysis of the absolute termolecular rate coefficients we are able to estimate the binding energy of CO to % MathType!MTEF!2!1!+- % feaafaart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaeyqaiaabw % hadaqhaaWcbaGaaGOmaaqaaiabgkHiTaaaaaa!397D! $$ {\rm{Au}}_2^ - $$ and % MathType!MTEF!2!1!+- % feaafaart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaeyqaiaabw % hadaqhaaWcbaGaaG4maaqaaiabgkHiTaaaaaa!397E! $$ {\rm{Au}}_3^ - $$ .