Role of vibrational anharmonicity in atmospheric radical hydrogen-bonded complexes.

نویسندگان

  • M Torrent-Sucarrat
  • J M Anglada
  • J M Luis
چکیده

Harmonic and anharmonic vibrational frequency calculations are reported for the most stable hydrogen bonded complexes formed between the hydroperoxyl radical and formic, acetic, nitric, and sulfuric acids which are of atmospheric interest. A comparison between the calculated IR spectra of the hydrogen bonded complexes with the corresponding separate monomers is also reported with the aim to facilitate a possible experimental identification of these complexes. The calculations have been carried out using the second-order vibrational perturbative treatment implemented by Barone applied to the PES obtained with the B3LYP functional using the 6-31+G(d,p) and 6-311+G(2d,2p) basis sets. Our calculations for the separate monomers predict vibrational frequencies with quite a good agreement with the experimental values. The anharmonic contribution results in differences of around 40 cm(-1) with respect to the harmonic values; although in some cases involving highly anharmonic modes, these differences can rise up to 300 and 450 cm(-1).

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Role of vibrational anharmonicity in atmospheric radical hydrogen-bonded complexesw

Harmonic and anharmonic vibrational frequency calculations are reported for the most stable hydrogen bonded complexes formed between the hydroperoxyl radical and formic, acetic, nitric, and sulfuric acids which are of atmospheric interest. A comparison between the calculated IR spectra of the hydrogen bonded complexes with the corresponding separate monomers is also reported with the aim to fac...

متن کامل

Ab Initio Theoretical Studies on the Kinetics of the Hydrogen Abstraction Reaction of Hydroxyl Radical with CH3CH2OCF2CHF2 (HFE-374pc2)

The hydrogen abstraction reaction of OH radical with CH3CH2OCF2CHF2 (HFE-374pc2) is investigated theoretically by semi-classical transition state theory. The stationary points on the potential energy surface of the reaction are located by using KMLYP density functional method along with 6-311++G(d,p) basis set. Vibrational anharmonicity coefficients, ...

متن کامل

Exploration of the potential energy surfaces, prediction of atmospheric concentrations, and prediction of vibrational spectra for the HO2...(H2O)n (n = 1-2) hydrogen bonded complexes.

The hydroperoxy radical (HO2) plays a critical role in Earth's atmospheric chemistry as a component of many important reactions. The self-reaction of hydroperoxy radicals in the gas phase is strongly affected by the presence of water vapor. In this work, we explore the potential energy surfaces of hydroperoxy radicals hydrogen bonded to one or two water molecules, and predict atmospheric concen...

متن کامل

Charge penetration and the origin of large O-H vibrational red-shifts in hydrated-electron clusters, (H2O)n-.

The origin of O-H vibrational red-shifts observed experimentally in (H2O)n(-) clusters is analyzed using electronic structure calculations, including natural bond orbital analysis. The red-shifts are shown to arise from significant charge transfer and strong donor-acceptor stabilization between the unpaired electron and O-H sigma* orbitals on a nearby water molecule in a double hydrogen-bond-ac...

متن کامل

Ultrafast Vibrational Dynamics of Hydrogen-Bonded Base Pairs and Hydrated DNA

.................................................................................................................................... 4 1 Hydrogen bonding ............................................................................................................... 7 1.1 The nature of the hydrogen bond ................................................................................... 7 1.2 Sub...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:
  • Physical chemistry chemical physics : PCCP

دوره 11 30  شماره 

صفحات  -

تاریخ انتشار 2009