The　mechanisms　of　the　reactions　of　the　radicals　(·OH　and　·NO2)　derived　from　peroxynitrous　acid　with　phenol　have　been　studied　using　density　functional　theory　(DFT)　at　the　B3LYP/6-311++G(d,　p)//B3LYP/6-311G(d,　p)　level.　The　geometries　of　all　the　molecules　were　optimized,　and　the　harmonic　vibration　frequencies　and　the　energies　were　calculated　as　well.　The　calculation　results　show　that　the　primary　products　of　the　reaction　of　peroxynitrous　acid　and　phenol　are　o-hydroxyphenol　and　p-hydroxyphenol,　due　to　their　relatively　lower　activation　barriers.　This　conclusion　is　in　agreement　with　the　corresponding　experimental　data.　In　addition,　the　effects　of　solvents　on　these　reactions　were　also　investigated.　The　results　suggest　that　polar　solvents　can　reduce　the　activation　energy　and　hence　facilitate　the　occurrence　of　reactions.　©　2006　Chinese　Chemical　Society　and　College　of　Chemistry　and　Molecular　Engineering,　Peking　University.