We derive a spin-dependent Hamiltonian that captures the symmetry of the zone edge states in silicon. We present analytical expressions of the spin-dependent states and of spin relaxation due to electron-phonon interactions in the multivalley conduction band. We find excellent agreement with experimental results. Similar to the usage of the Kane Hamiltonian in direct band-gap semiconductors, the new Hamiltonian can be used to study spin properties of electrons in silicon.PACS numbers: 78.60.Fi, 71.70.Ej Silicon is an ideal material choice for spintronics due to its relatively long spin relaxation time and central role in semiconductor technology. These characteristics are the reason for the wide interest in recent spin injection experiments [1][2][3][4]. To date, however, modeling of basic spin properties in silicon required elaborate numerical methods [5]. Notably, the availability of transparent spin-dependent theories in direct gap semiconductors have spurred the field of semiconductor spintronics [6]. The importance of a lucid theory that accurately describes spin properties of conduction electrons in silicon with relatively simple means is thus clear.In the first part of this letter we derive a Hamiltonian that captures spin properties of conduction electrons in silicon. The Hamiltonian is constructed by its invariance to the symmetry operations of the space group, G 2 32 , which describes the symmetry of the X-point at the edge of the Brillouin zone [7,8]. In silicon the X-point is closer to the absolute conduction band minimum than all other high symmetry points. While k·p and tight-binding models have been available for many decades [9][10][11][12][13][14][15][16][17], spin has heretofore been ignored since spin-orbit coupling in Si is weak [18][19][20][21][22] and lattice inversion symmetry causes spin degeneracy. The present work is motivated by the emergence of experimental work on spin-polarized electron transport in silicon [1][2][3][4].In the second part, this Hamiltonian is used to elucidate the nature of intravalley and intervalley spin relaxation processes in silicon due to electron-phonon interactions. Our approach unravels the underlying physics, structure and symmetries of dominant spin-flip mechanisms. These insights cannot be shown by state-of-the art numerical studies in which only the magnitude and temperature dependence are calculated [5]. We derive analytical forms and selection rules of the dominant spin-flip matrix elements and explain the subtle distinction between spin and momentum scattering processes. Importantly, it is shown that spin relaxation due to intravalley scattering is caused by coupling of the lower and upper conduction bands (whereas intravalley momentum relaxation is governed by dilation and uniaxial deformation potentials of the lower conduction band). The accepted