1980
DOI: 10.1007/978-1-4899-2891-7
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The Tunnel Effect in Chemistry

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Cited by 937 publications
(911 citation statements)
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“…In a hydride shift the distance traveled by the proton is small, comparable to the range of its wave character, so we have investigated the possibility that there is a quantum-mechanical tunneling process involved (9). We find that there is indeed tunneling accompanying thermal excitation on the way to the TS (Fig.…”
Section: Methodsmentioning
confidence: 97%
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“…In a hydride shift the distance traveled by the proton is small, comparable to the range of its wave character, so we have investigated the possibility that there is a quantum-mechanical tunneling process involved (9). We find that there is indeed tunneling accompanying thermal excitation on the way to the TS (Fig.…”
Section: Methodsmentioning
confidence: 97%
“…E a values were obtained from the slopes in the plots of lnk vs. 1/T in Fig. 2 using the Arrhenius equation k = A exp(−E a /RT) (9). E a(H) was 35.4 kJ·mol −1 while E a(D) was 44.5 kJ·mol −1 , so the difference of 9.1 kJ·mol −1 is well in excess of 5.0 kJ·mol −1 , consistent with a tunneling process.…”
Section: Methodsmentioning
confidence: 99%
“…Because the de Broglie wavelength is inversely proportional to particle momentum, tunneling becomes noticeable in small masses and at low temperatures. The de Broglie wavelengths for hydrogen (H, 9.8-1.8 Å) and deuterium (D, 6.9-1.3 Å) at 10-300 K exceed the scale of the typical widths of activation barriers in chemical reactions (∼1 Å), which invalidates a purely classical description of their motion in chemistry (1,2). Hydrogen, including its ionic forms (H + and H − ), is present in water and most organic compounds, and kinetic measurements have established that tunneling occurs in reactions involving hydrogen in gas (1), liquid (1,3,4), and solid phases (4).…”
mentioning
confidence: 99%
“…The de Broglie wavelengths for hydrogen (H, 9.8-1.8 Å) and deuterium (D, 6.9-1.3 Å) at 10-300 K exceed the scale of the typical widths of activation barriers in chemical reactions (∼1 Å), which invalidates a purely classical description of their motion in chemistry (1,2). Hydrogen, including its ionic forms (H + and H − ), is present in water and most organic compounds, and kinetic measurements have established that tunneling occurs in reactions involving hydrogen in gas (1), liquid (1,3,4), and solid phases (4). Tunneling has also been recognized as a significant factor in reactions on surfaces and at interfaces; for example, proton transfer reactions at the air/water interface (5) and enzyme catalysis (3,6).…”
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